Coating compositions having improved scratch resistance, coated substrates and methods related thereto

ABSTRACT

Compositions are provided which contain (a) one or more polysiloxanes comprising at least one reactive functional group; a plurality of particles; and, optionally, one or more curing agents comprising at least one functional group that is reactive with any reactive functional group of polysiloxane (a). Additionally, a process for applying the multi-component composite coatings described above to a substrate and coated substrates are provided. A process for preparing the coating compositions also is provided. The multi-component composite coating compositions of the invention provide highly scratch resistant color-plus-clearcoatings capable of retaining scratch resistance after weathering.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application No.09/629,444 filed Jul. 31, 2000, now U.S. Pat. No. 6,657,001, which is aContinuation-in-Part application of U.S. patent application Ser. No.09/489,042 filed Jan. 21, 2000 now Abandoned, which is aContinuation-in-Part application of U.S. patent application Ser. No.09/365,069 filed Jul. 30, 1999 now Abandoned. U.S. patent applicationSer. No. 09/489,042 claims the benefit of priority from ProvisionalPatent Application Serial No. 60/171,899 filed Dec. 23, 1999.

FIELD OF THE INVENTION

Certain embodiments of the present invention are directed tocompositions comprising at least one polysiloxane comprising at leastone reactive functional group, and a plurality of particles. Embodimentsof the present invention also are directed to compositions comprising atleast one polysiloxane comprising at least one reactive functionalgroup, at least one reactant comprising at least one functional groupthat is reactive with at least one functional group selected from the atleast one functional group of the at least one polysiloxane and at leastone functional group of the at least one reactant, and a plurality ofparticles. Other embodiments of the present invention are directed tosubstrates coated with the aforementioned compositions. Furtherembodiments of the present invention are directed to methods forimproving scratch resistance of a substrate. It will be apparent to oneof ordinary skill in the art that specific embodiments of the presentinvention may be directed to some or all of these aspects of the presentinvention as well as other desirable aspects.

BACKGROUND OF THE INVENTION

Color-plus-clearcoating systems involving the application of a coloredor pigmented basecoat to a substrate followed by application of atransparent or clearcoat over at least a portion of the basecoat havebecome increasingly popular as original finishes for a number ofconsumer products including, for example, automotive vehicles. Thecolor-plus-clearcoating systems have outstanding appearance propertiessuch as gloss and distinctness of image, due in large part to theclearcoat. Such color-plus-clearcoating systems have become popular foruse with automotive vehicles, aerospace applications, floor coveringssuch as ceramic tiles and wood flooring, packaging coatings and thelike.

Topcoat film-forming compositions, particularly those used to form thetransparent clearcoat in color-plus-clearcoating systems for automotiveapplications, are subject to defects that occur during the assemblyprocess as well as damage from numerous environmental elements. Suchdefects during the assembly process include paint defects in theapplication or curing of the basecoat or the clearcoat. Damagingenvironmental elements include acidic precipitation, exposure toultraviolet radiation from sunlight, high relative humidity and hightemperatures, defects due to contact with objects causing scratching ofthe coated surface, and defects due to impact with small, hard objectsresulting in chipping of the coating surface.

Typically, a harder more highly crosslinked film may exhibit improvedscratch resistance, but it is less flexible and much more susceptible tochipping or thermal cracking due to embrittlement of the film resultingfrom a high crosslink density. A softer, less crosslinked film, whilenot prone to chipping or thermal cracking, is susceptible to scratching,waterspotting, and acid etch due to a low crosslink density of the curedfilm.

Further, elastomeric automotive parts and accessories, for example,elastomeric bumpers and hoods, are typically coated “off site” andshipped to automobile assembly plants. The coating compositions appliedto such elastomeric substrates are typically formulated to be veryflexible so the coating can bend or flex with the substrate withoutcracking. To achieve the requisite flexibility, coating compositions foruse on elastomeric substrates often are formulated to produce coatingswith lower crosslink densities or to include flexibilizing adjuvantswhich act to lower the overall film glass transition temperature (Tg).While acceptable flexibility properties can be achieved with theseformulating techniques, they also can result in softer films that aresusceptible to scratching. Consequently, great expense and care must betaken to package the coated parts to prevent scratching of the coatedsurfaces during shipping to automobile assembly plants.

A number of patents teach the use of a coating comprising a dispersionof colloidal silica in an alcohol-water solution of a partial condensateof a silanol of the formula RSi(OH)₃ wherein at least 70 weight percentof the partial condensate is the partial condensate of CH₃Si(OH)₃.Representative, nonlimiting examples are U.S. Pat. Nos. 3,986,997,4,027,073, 4,239,738, 4,310,600 and 4,410,594.

U.S. Pat. No. 4,822,828 teaches the use of a vinyl functional silane inan aqueous, radiation curable, coating composition which comprises: (a)from 50 to 85 percent, based on the total weight of the dispersion, of avinyl functional silane, (b) from 15 to 50 percent, based on the totalweight of the dispersion of a multifunctional acrylate, and (c)optionally, from 1 to 3 weight percent of a photoinitiator. Thevinyl-functional silane is the partial condensate of silica and asilane, such that at least sixty percent of the silane is avinyl-functional silane conforming to the formula(R)_(a)Si(R′)_(b)(R″)_(c) wherein R is allyl or vinyl functional alkyl;R′ is hydrolyzable alkoxy or methoxy; R″ is non-hydrolyzable, saturatedalkyl, phenyl, or siloxy, such that a+b+c=4; and a≧1; b≧1; c≧0. Thepatent discloses that these coating compositions may be applied toplastic materials and cured by exposure to ultraviolet or electron beamirradiation to form a substantially clear, abrasion resistant layer.

U.S. Pat. No. 5,154,759 teaches a polish formulation comprising areactive amine functional silicone polymer and at least one otheringredient normally used in polish formulations. One such ingredientdisclosed in the patent is an abrasive, which is taught to be aluminumsilicate, diatomaceous earth, pumice, fuller's earth, bentonite, silica,tripoli, hydrated calcium silicate, chalk, colloidal clay, magnesiumoxide, red iron oxide, or tin oxide.

U.S. Pat. No. 5,686,012 describes modified particles comprisinginorganic colored or magnetic particles as core particles, and at leastone polysiloxane modified with at least one organic group which iscoated on the surfaces of the core particles. The patent also disclosesa water based paint comprising a paint base material and the modifiedparticles as the pigment as well as a process for producing the modifiedparticles.

U.S. Pat. No. 5,853,809 discloses clearcoats in color-plus-clear systemswhich have improved scratch resistance due to the inclusion in thecoating composition of inorganic particles such as colloidal silicaswhich have been surface modified with a reactive coupling agent viacovalent bonding.

Despite recent improvements in color-plus-clearcoating systems, thereremains a need in the automotive coatings art for topcoats having goodinitial scratch resistance as well as enhanced retained scratchresistance without embrittlement of the film due to high crosslinkdensity. Moreover, it would be advantageous to provide topcoats forelastomeric substrates utilized in the automotive industry which areboth flexible and resistant to scratching.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to compositionsformed from components comprising:

(a) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

 wherein each R¹, which may be identical or different, represents H, OH,a monovalent hydrocarbon group or a monovalent siloxane group; each R²,which may be identical or different, represents a group comprising atleast one reactive functional group; wherein m and n fulfill therequirements of 0<n<4, 0<m<4 and 2≦(m+n)<4;

(b) at least one reactant comprising at least one functional group thatis reactive with at least one functional group selected from the atleast one functional group of the at least one polysiloxane and at leastone functional group of the at least one reactant; and

(c) a plurality of particles selected from inorganic particles,composite particles, and mixtures thereof, wherein each component isdifferent.

In another embodiment, the present invention is directed to compositionsformed from components comprising:

(a) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

 wherein each R¹, which may be identical or different, represents H, OH,a monovalent hydrocarbon group or a monovalent siloxane group; each R²,which may be identical or different, represents a group comprising atleast one reactive functional group; wherein m and n fulfill therequirements of 0<n<4, 0<m<4 and 2≦(m+n)<4;

(b) at least one reactant comprising at least one functional group thatis reactive with at least one functional group selected from the atleast one functional group of the at least one polysiloxane and at leastone functional group of the at least one reactant; and

(c) a plurality of particles,

wherein each component is different, and

wherein a retained scratch resistance of the composition when cured isgreater than a retained scratch resistance of a composition when curedthat does not contain the plurality of particles and wherein eachcomponent is different.

In still another embodiment, the present invention is directed tocompositions formed from components comprising:

(a) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

 wherein each R¹, which may be identical or different, represents H, OH,a monovalent hydrocarbon group or a monovalent siloxane group; each R²,which may be identical or different, represents a group comprising atleast one reactive functional group; wherein m and n fulfill therequirements of 0<n<4, 0<m<4 and 2≦(m+n)≦4;

 and provided that when the at least one polysiloxane is a partialcondensate of a silanol, then less than 70% by weight of the partialcondensate is the partial condensate of CH₃Si(OH)₃; and

(b) a plurality of particles having an average particle size of lessthan 100 nanometers prior to incorporation into the composition, whereineach component is different.

In a further embodiment, the present invention is directed to a powdercomposition formed from components comprising:

(a) at least one surface active agent comprising:

(i) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

 wherein each R¹, which may be identical or different, represents H, OH,a monovalent hydrocarbon group or a monovalent siloxane group; each R²,which may be identical or different, represents a group comprising atleast one reactive functional group, wherein m and n fulfill therequirements of 0<n<4, 0<m<4 and 2≦(m+n)≦4; and

(ii) at least one polyacrylate surface active agent having at least onefunctional group selected from amino and hydroxyl functionality, acidfunctionality and acid and hydroxyl functionality; and

(b) a plurality of particles, wherein each component is different.

Additionally, a coated substrate is disclosed to be within the scope ofthe present invention which comprises a substrate and a compositioncoated over at least a portion of the substrate, the composition beingany of the foregoing compositions according to the present invention.The present invention also provides a method of coating a substratewhich comprises applying over at least a portion of the substrate acomposition, the composition being any of the foregoing compositionsaccording to the present invention. A coated substrate also is providedwhich comprises a substrate and a composition coated over at least aportion of the substrate, the composition being any of the foregoingcompositions according to the present invention. Coated automotivesubstrates also are disclosed to be within the present invention whichcomprise an automotive substrate which is coated, at least in part, byany of the foregoing compositions according to the present invention.The present invention also provides methods of making coated automotivesubstrates comprising obtaining an automotive substrate and applyingover at least a portion of the automotive substrate any of the foregoingcompositions according to the present invention.

Also provided are multi-component composite coating compositions whichcomprise a basecoat deposited from a pigmented coating composition, andany one of the foregoing topcoating compositions according to thepresent invention applied over at least a portion of the basecoat. Thepresent invention also provides methods for making multi-componentcomposite coating compositions comprising: (a) applying a pigmentedcomposition to a substrate to form a basecoat; and (b) applying atopcoating composition over at least a portion of the basecoat to form atopcoat thereon, the topcoating composition being any of the foregoingcompositions according to the present invention. The topcoatingcomposition can be cured. In one embodiment, the coating composition isthermally cured after application to the substrate. In anotherembodiment, the coating composition is cured by exposure to ionizingradiation after application to the substrate. In yet another embodiment,the coating composition is cured by exposure to actinic radiation afterapplication to the substrate, while in another embodiment the coatingcomposition is cured by exposure to (1) ionizing radiation or actinicradiation and (2) thermal energy after application to the substrate.

Methods of improving the scratch resistance of a polymeric substrate orpolymeric coating which comprise applying to the polymeric substrate orpolymeric coating any of the foregoing compositions according to thepresent invention also are provided in another embodiment of the presentinvention. The present invention also provides methods for retaining thegloss of a polymeric substrate or polymeric coating over time whichcomprises applying to at least a portion of the polymeric substrate orpolymeric coating any of the foregoing compositions according to thepresent invention. Also provided are methods for revitalizing the glossof a polymeric substrate or polymeric coating comprising applying to atleast a portion of the polymeric substrate or polymeric coating any ofthe foregoing compositions according to the present invention.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is a transmission electron micrograph (30,000× magnification) ofa cross-section of a cured transparent topcoating composition of thepresent invention which contains both colloidal silica and polysiloxane;

FIG. 2 is a transmission electron micrograph (30,000× magnification) ofa cross-section of a comparative example of a transparent topcoatingcomposition which contains colloidal silica but not polysiloxane;

FIG. 3 is a transmission electron micrograph of a cross-section of thecured transparent topcoating composition of FIG. 1, but viewed at54,000× magnification;

FIG. 4 is a transmission electron micrograph (105,000× magnification) ofa cross-section of a cured transparent topcoating composition of thepresent invention which included a preformed dispersion of colloidalsilica and polysiloxane;

FIG. 5 is a graph of scratch depth as a function of load over a givenscratch distance showing scratch (mar) resistance of a commercialtwo-component polyurethane coating; and

FIG. 6 is a graph of scratch depth as a function of load over a givenscratch distance showing scratch (mar) resistance of a two-componentcoating containing colloidal silica and polysiloxane of the presentinvention.

FIG. 7 is a transmission electron micrograph (105,000× magnification) ofa cross-section of a cured transparent topcoating composition of thepresent invention, taken generally perpendicular to the surface of thecoating, which included a preformed polysiloxane dispersion comprising2% colloidal silica.

FIG. 8 is a transmission electron micrograph (105,000× magnification) ofa cross-section of a cured transparent topcoating composition of thepresent invention, taken at an angle with respect to the surface of thecoating, which included a preformed polysiloxane dispersion comprising2% colloidal silica.

FIG. 9 is a transmission electron micrograph (105,000× magnification) ofa cross-section of a cured transparent topcoating composition of thepresent invention, taken generally perpendicular to the surface of thecoating, which included a preformed polysiloxane dispersion comprising8.5% colloidal silica.

FIG. 10 is a transmission electron micrograph (105,000× magnification)of a cross-section of a cured transparent topcoating composition of thepresent invention, taken at an angle with respect to the surface of thecoating, which included a preformed polysiloxane dispersion comprising8.5% colloidal silica.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In one embodiment, the present invention is directed to a compositionformed from components comprising: (a) at least one polysiloxanecomprising at least one reactive functional group, the at least onepolysiloxane comprising at least one of the following structural units(I)

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

wherein R¹, R², m, and n are as described above for that structure; (b)at least one reactant comprising at least one functional group that isreactive with at least one functional group selected from the at leastone functional group of the at least one polysiloxane and at least onefunctional group of the at least one reactant; and (c) a plurality ofparticles selected from inorganic particles, composite particles, andmixtures thereof, wherein each component is different.

It should be understood that the “at least one polysiloxane comprisingat least one structural unit (I)” above is a polymer that contains atleast two Si atoms per molecule. As used herein, the term “polymer” inmeant to encompass oligomer, and includes without limitation bothhomopolymers and copolymers. It should also be understood that the atleast one polysiloxane can include linear, branched, dendritic or cyclicpolysiloxanes.

Moreover, as used herein, “formed from” denotes open, e.g.,“comprising,” claim language. As such, it is intended that a composition“formed from” a list of recited components be a composition comprisingat least these recited components, and can further comprise other,nonrecited components, during the composition's formation.

Also, as used herein, the term “reactive” refers to a functional groupthat forms a covalent bond with another functional group underconditions sufficient to cure the composition.

Each of m and n depicted in the at least one structural unit (I) abovefulfill the requirements of 0<n<4, 0<m<4 and 2≦(m+n)≦4. When (m+n) is 3,the value represented by n can be 2 and the value represented by m is 1.Likewise, when (m+n) is 2, the value represented by each of n and m is1.

In a further embodiment, the present invention is directed to curedcompositions as previously described wherein at least one reactant ispresent during the formation of the coating composition. As used herein,the “at least one reactant” refers to any material comprising afunctional group that is reactive with at least one functional groupselected from at least one functional group of the at least onepolysiloxane and at least one functional group of the material. In oneembodiment, the at least one reactant can be selected from at least onecuring agent.

In another embodiment, the present invention is directed to acomposition formed from components comprising (a) at least onepolysiloxane comprising at least one reactive functional group, the atleast one polysiloxane comprising at least one of the followingstructural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

wherein R¹, R², m, and n are as described above for that structure; (b)at least one reactant comprising at least one functional group that isreactive with with at least one functional group selected from the atleast one functional group of the at least one polysiloxane and at leastone functional group of the at least one reactant; and (c) a pluralityof particles, wherein each component is different and wherein a retainedscratch resistance of the composition when cured is improved whencompared to the retained scratch resistance of a composition when curedthat does not contain the plurality of particles.

The term “retained scratch resistance” referred to throughout thespecification and the appended claims will be described in detail below.

As used herein, the phrase “each component is different” refers tocomponents which do not have the same chemical structure as othercomponents in the composition.

As used herein, the term “cure” as used in connection with acomposition, e.g., “a cured composition,” shall mean that anycrosslinkable components of the composition are at least partiallycrosslinked. In certain embodiments of the present invention, thecrosslink density of the crosslinkable components, i.e., the degree ofcrosslinking, ranges from 5% to 100% of complete crosslinking. In otherembodiments, the crosslink density ranges from 35% to 85% of fullcrosslinking. In other embodiments, the crosslink density ranges from50% to 85% of full crosslinking.

One skilled in the art will understand that the presence and degree ofcrosslinking, i.e., the crosslink density, can be determined by avariety of methods, such as dynamic mechanical thermal analysis (DMTA)using a TA Instruments DMA 2980 DMTA analyzer conducted under nitrogen.This method determines the glass transition temperature and crosslinkdensity of free films of coatings or polymers. These physical propertiesof a cured material are related to the structure of the crosslinkednetwork.

According to this method, the length, width, and thickness of a sampleto be analyzed are first measured, the sample is tightly mounted to thePolymer Laboratories MK III apparatus, and the dimensional measurementsare entered into the apparatus. A thermal scan is run at a heating rateof 3° C./min, a frequency of 1 Hz, a strain of 120%, and a static forceof 0.01 N, and sample measurements occur every two seconds. The mode ofdeformation, glass transition temperature, and crosslink density of thesample can be determined according to this method. Higher crosslinkdensity values indicate a higher degree of crosslinking in the coating.

In another embodiment, the present invention is directed to acomposition as described above, wherein R², which may be identical ordifferent, represents a group comprising at least one reactivefunctional group selected from a hydroxyl group, a carboxyl group, anisocyanate group, a blocked polyisocyanate group, a primary amine group,a secondary amine group, an amide group, a carbamate group, a ureagroup, a urethane group, a vinyl group, an unsaturated ester group suchas an acrylate group and a methacrylate group, a maleimide group, afumarate group, an onium salt group such as a sulfonium group and anammonium group, an anhydride group, a hydroxy alkylamide group, and anepoxy group. Non-limiting examples of blocked polyisocyanate groupsinclude those derived from hexamethylene diisocyante (HDI), isopheronediisocyante (IPDI), and triazine derived isocyanates such astrisaminocarbonyl triisocanyurate TACT.

In another embodiment, the present invention is directed to acomposition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I):

R¹ _(n)R² _(m)SiO_((4−n−m)/2)

 wherein each substituent group R¹, which may be identical or different,represents a group selected from H, OH, a monovalent hydrocarbon group,and a monovalent siloxane group; each substituent group R², which may beidentical or different, represents a group comprising at least onereactive functional group selected from a hydroxyl group, a carboxylgroup, an isocyanate group, a blocked polyisocyanate group, a primaryamine group, a secondary amine group, an amide group, a carbamate group,a urea group, a urethane group, a vinyl group, an unsaturated estergroup such as an acrylate group and a methacrylate group, a maleimidegroup, a fumarate group, an onium salt group such as a sulfonium groupand an ammonium group, an anhydride group, a hydroxy alkylamide group,and an epoxy group; wherein m and n fulfill the requirements of 0<n<4,0<m<4 and 2≦(m+n)≦4; and provided that when the at least onepolysiloxane is a partial condensate of a silanol, then less than 70% byweight of the partial condensate is the partial condensate ofCH₃Si(OH)₃; and

(b) a plurality of having an average particle size of less than 100nanometers prior to incorporation into the composition, wherein eachcomponent is different.

As used herein, a “monovalent hydrocarbon group” means a monovalentgroup having a backbone repeat unit based exclusively on carbon. As usedherein, “monovalent” refers to a substituent group that, as asubstituent group, forms only one single, covalent bond. For example, amonovalent group on the at least one polysiloxane will form one singlecovalent bond to a silicon atom in the backbone of the at least onepolysiloxane polymer. As used herein, “hydrocarbon groups” are intendedto encompass both branched and unbranched hydrocarbon groups.

Thus, when referring to a “monovalent hydrocarbon group,” thehydrocarbon group can be branched or unbranched, acyclic or cyclic,saturated or unsaturated, or aromatic, and can contain from 1 to 24 (orin the case of an aromatic group from 3 to 24) carbon atoms. Nonlimitingexamples of such hydrocarbon groups include alkyl, alkoxy, aryl,alkaryl, and alkoxyaryl groups. Nonlimiting examples of lower alkylgroups include, for example, methyl, ethyl, propyl, and butyl groups. Asused herein, “lower alkyl” refers to alkyl groups having from 1 to 6carbon atoms. One or more of the hydrogen atoms of the hydrocarbon canbe substituted with heteroatoms. As used herein, “heteroatoms” meanselements other than carbon, for example, oxygen, nitrogen, and halogenatoms.

As used herein, “siloxane” means a group comprising a backbonecomprising two or more —SiO— groups. For example, the siloxane groupsrepresented by R¹, which is discussed above, and R, which is discussedbelow, can be branched or unbranched, and linear or cyclic. The siloxanegroups can be substituted with pendant organic substituent groups, forexample, alkyl, aryl, and alkaryl groups. The organic substituent groupscan be substituted with heteroatoms, for example oxygen, nitrogen, andhalogen atoms, reactive functional groups, for example those reactivefunctional groups discussed above with reference to R², and mixtures ofany of the foregoing.

In another embodiment, the present invention is directed to acomposition as previously described, wherein the at least one reactantis selected from at least one curing agent.

In one embodiment, the present invention is directed to a composition aspreviously described, wherein the at least one polysiloxane comprises atleast two reactive functional groups. The at least one polysiloxane canhave a reactive group equivalent weight ranging from 50 to 1000 mg pergram of the at least one polysiloxane. In one embodiment, the at leastone polysiloxane has a hydroxyl group equivalent weight ranging from 50to 1000 mg KOH per gram of the at least one polysiloxane. In anotherembodiment, the at least one polysiloxane has a hydroxyl groupequivalent weight ranging from 100 to 300 mg KOH per gram of the atleast one polysiloxane, while in another embodiment, the hydroxyl groupequivalent weight ranges from 100 to 500 mg KOH per gram. The hydroxylequivalent weight may range between any combination of these valuesinclusive of the recited values.

In another embodiment, the present invention is directed to acomposition as previously described, wherein at least one R² grouprepresents a group comprising at least one reactive functional groupselected from a hydroxyl group and a carbamate group. In yet anotherembodiment, the present invention is directed to a composition aspreviously described, wherein at least one R² group represents a groupcomprising at least two reactive functional groups selected from ahydroxyl group and a carbamate group. In another embodiment, the presentinvention is directed to a composition as previously described, whereinat least one R² group represents a group comprising an oxyalkylene groupand at least two hydroxyl groups.

In one embodiment, the present invention is directed to a curedcomposition as previously described in which the at least onepolysiloxane comprises reactive functional groups which are thermallycurable functional groups. In an alternative embodiment, at least one ofthe reactive functional groups of the polysiloxane can be curable byionizing radiation or actinic radiation. In another alternativeembodiment, the polysiloxane can comprise at least one functional groupwhich is curable by thermal energy and at least one functional groupwhich is curable by ionizing or actinic radiation.

As used herein, “ionizing radiation” means high energy radiation and/orthe secondary energies resulting from conversion of this electron orother particle energy to neutron or gamma radiation, said energies beingat least 30,000 electron volts and can range from 50,000 to 300,000electron volts. While various types of ionizing irradiation are suitablefor this purpose, such as X-ray, gamma and beta rays, the radiationproduced by accelerated high energy electrons or electron beam devicesis preferred. The amount of ionizing radiation in rads for curingcompositions according to the present invention can vary based upon sucha factors as the components of the coating formulation, the thickness ofthe coating upon the substrate, the temperature of the coatingcomposition and the like. Generally, a 1 mil (25 micrometer) thick wetfilm of a coating composition according to the present invention can becured in the presence of oxygen through its thickness to a tack-freestate upon exposure to from 0.5 to 5 megarads of ionizing radiation.

“Actinic radiation” is light with wavelengths of electromagneticradiation ranging from the ultraviolet (“UV”) light range, through thevisible light range, and into the infrared range. Actinic radiationwhich can be used to cure coating compositions of the present inventiongenerally has wavelengths of electromagnetic radiation ranging from 150to 2,000 nanometers (nm), can range from 180 to 1,000 nm, and also canrange from 200 to 500 nm. Examples of suitable ultraviolet light sourcesinclude mercury arcs, carbon arcs, low, medium or high pressure mercurylamps, swirl-flow plasma arcs and ultraviolet light emitting diodes.Preferred ultraviolet light-emitting lamps are medium pressure mercuryvapor lamps having outputs ranging from 200 to 600 watts per inch (79 to237 watts per centimeter) across the length of the lamp tube. Generally,a 1 mil (25 micrometer) thick wet film of a coating compositionaccording to the present invention can be cured through its thickness toa tack-free state upon exposure to actinic radiation by passing the filmat a rate of 20 to 1000 feet per minute (6 to 300 meters per minute)under four medium pressure mercury vapor lamps of exposure at 200 to1000 millijoules per square centimeter of the wet film.

Useful radiation-curable groups which can be present as reactivefunctional groups on the polysiloxane include unsaturated groups such asvinyl groups, acrylate groups, methacrylate groups, ethacrylate groups,epoxy groups such as cycloaliphatic epoxy groups. In one embodiment, theUV curable groups can include acrylate groups, maleimides, fumarates,and vinyl ethers.

In one embodiment, the present invention is directed to a composition aspreviously described wherein the at least one polysiloxane (a) has thefollowing structure (II) or (III):

wherein: m has a value of at least 1; m′ ranges from 0 to 75; n rangesfrom 0 to 75; n′ ranges from 0 to 75; each R, which may be identical ordifferent, is selected from H, OH, a monovalent hydrocarbon group, amonovalent siloxane group, and mixtures of any of the foregoing; and—R^(a) comprises the following structure (IV):

—R³—X  (IV)

 wherein —R³ is selected from an alkylene group, an oxyalkylene group,an alkylene aryl group, an alkenylene group, an oxyalkenylene group, andan alkenylene aryl group; and X represents a group which comprises atleast one reactive functional group selected from a hydroxyl group, acarboxyl group, an isocyanate group, a blocked polyisocyanate group, aprimary amine group, a secondary amine group, an amide group, acarbamate group, a urea group, a urethane group, a vinyl group, anunsaturated ester group such as an acrylate group and a methacrylategroup, a maleimide group, a fumarate group, an onium salt group such asa sulfonium group and an ammonium group, an anhydride group, a hydroxyalkylamide group, and an epoxy group.

As used herein, “alkylene” refers to an acyclic or cyclic, saturatedhydrocarbon group having a carbon chain length of from C₂ to C₂₅.Nonlimiting examples of suitable alkylene groups include, but are notlimited to, those derived from propenyl, 1-butenyl, 1-pentenyl,1-decenyl, and 1-heneicosenyl, such as, for example (CH₂)₃, (CH₂)₄,(CH₂)₅, (CH₂)₁₀, and (CH₂)₂₃, respectively, as well as isoprene andmyrcene.

As used herein, “oxyalkylene” refers to an alkylene group containing atleast one oxygen atom bonded to, and interposed between, two carbonatoms and having an alkylene carbon chain length of from C₂ to C₂₅.Nonlimiting examples of suitable oxyalkylene groups include thosederived from trimethylolpropane monoallyl ether, trimethylolpropanediallyl ether, pentaerythritol monoallyl ether, polyethoxylated allylalcohol, and polypropoxylated allyl alcohol, such as—(CH₂)₃OCH₂C(CH₂OH)₂(CH₂CH₂—).

As used herein, “alkylene aryl” refers to an acyclic alkylene groupsubstituted with at least one aryl group, for example, phenyl, andhaving an alkylene carbon chain length of C₂ to C₂₅. The aryl group canbe further substituted, if desired. Nonlimiting examples of suitablesubstituent groups for the aryl group include, but are not limited to,hydroxyl groups, benzyl groups, carboxylic acid groups, and aliphatichydrocarbon groups. Nonlimiting examples of suitable alkylene arylgroups include, but are not limited to, those derived from styrene and3-isopropenyl-∝,∝-dimethylbenzyl isocyanate, such as —(CH₂)₂C₆H₄— and—CH₂CH(CH₃)C₆H₃(C(CH₃)₂(NCO). As used herein, “alkenylene” refers to anacyclic or cyclic hydrocarbon group having one or more double bonds andhaving an alkenylene carbon chain length of C₂ to C₂₅. Nonlimitingexamples of suitable alkenylene groups include those derived frompropargyl alcohol and acetylenic diols, for example,2,4,7,9-tetramethyl-5-decyne-4,7-diol which is commercially availablefrom Air Products and Chemicals, Inc. of Allentown, Pa. as SURFYNOL 104.

Formulae (II) and (III) are diagrammatic, and are not intended to implythat the parenthetical portions are necessarily blocks, although blocksmay be used where desired. In some cases the polysiloxane may comprise avariety of siloxane units. This is increasingly true as the number ofsiloxane units employed increases, and especially true when mixtures ofa number of different siloxane units are used. In those instances wherea plurality of siloxane units are used and it is desired to form blocks,oligomers can be formed which can be joined to form the block compound.By judicious choice of reactants, compounds having an alternatingstructure or blocks of alternating structure may be used.

In yet another embodiment, the present invention is directed to anycomposition as previously described, wherein the particles are differentfrom the at least one polysiloxane. In yet another embodiment, thepresent invention is directed to any composition as previouslydescribed, wherein the particles have an average particle size less than100 nanometers prior to incorporation into the composition. Methodsknown to one of ordinary skill in the art for measuring the averageparticle size are discussed in detail below.

In one embodiment, the present invention is directed to a composition aspreviously described wherein the substituent group R³ represents anoxyalkylene group. In another embodiment, R³ represents an oxyalkylenegroup, and X represents a group which comprises at least two reactivefunctional groups.

In another embodiment, the present invention is directed to anycomposition as previously described comprising at least one polysiloxanehaving the structure (II) or (III) described above, wherein (n+m) rangesfrom 2 to 9. In yet another embodiment, in compositions comprising atleast one polysiloxane having the structure (II) or (III) describedabove, (n+m) ranges from 2 to 3. In another embodiment, in compositionscomprising at least one polysiloxane having the structure (II) or (III)described above, (n′+m′) ranges from 2 to 9. In another embodiment, incompositions comprising at least one polysiloxane having the structure(II) or (III) described above, (n′+m′) ranges from 2 to 3.

In one embodiment, the present invention is directed to any compositionas previously described wherein X represents a group comprising at leastone reactive functional group selected from a hydroxyl group and acarbamate group. In another embodiment, the present invention isdirected to composition as previously described wherein X represents agroup which comprises at least two hydroxyl groups. In yet anotherembodiment, the present invention is directed to any composition aspreviously described wherein X represents a group which comprises atleast one group selected from H, a monohydroxy-substituted organicgroup, and a group having the following structure (V):

R⁴—(CH₂—OH)_(p)  (V)

wherein the substituent group R⁴ represents

when p is 2 and the substituent group R³ represents a C₁ to C₄ alkylenegroup, or

the substituent group R⁴ represents

when p is 3.

wherein at least a portion of X represents a group having the structure(V). In another embodiment, the present invention is directed to anycomposition as previously described wherein m is 2 and p is 2.

In one embodiment, the present invention is directed to any compositionas previously described comprising at least one polysiloxane having thestructure (II) or (III), wherein, if no curing agent is present, and ifthe at least one polysiloxane is a partial condensate of a silanol, thenless than 70% by weight of the partial condensate is the partialcondensate of CH₃Si(OH)₃. These components used in these variousembodiments can be selected from the coating components discussed above.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount ranging from 0.01 to 90 weight percent based ontotal weight of the resin solids of the components which form thecomposition. In another embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount from at least 2weight percent based on total weight of the resin solids of thecomponents which form the composition. In another embodiment, thepresent invention is directed to compositions as previously describedwherein the at least one polysiloxane (a), when added to the othercomponent(s) of the composition, is present in the composition in anamount from at least 5 weight percent based on total weight ofcomponents which form the composition. In yet another embodiment, thepresent invention is directed to compositions as previously describedwherein the at least one polysiloxane (a), when added to the othercomponent(s) of the composition, is present in the composition in anamount from at least 10 weight percent based on total weight of theresin solids of the components which form the composition.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount less than 90 weight percent based on totalweight of the resin solids of the components which form the composition.In another embodiment, the present invention is directed to compositionsas previously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount less than 80 weight percent based on totalweight of the resin solids of the components which form the composition.In another embodiment, the present invention is directed to compositionsas previously described wherein the at least one polysiloxane (a), whenadded to the other component(s) of the composition, is present in thecomposition in an amount less than 65 weight percent based on totalweight of the resin solids of the components which form the composition.In yet another embodiment, the present invention is directed tocompositions as previously described wherein the at least onepolysiloxane (a), when added to the other component(s) of thecomposition, is present in the composition in an amount less than 30weight percent based on total weight of the resin solids of thecomponents which form the composition. The amount of at least onepolysiloxane (a) may range between any combination of these valuesinclusive of the recited values.

As used herein “based on total weight of the resin solids” of thecomponents which form the composition means that the amount of thecomponent added during the formation of the composition is based uponthe total weight of the solids (non-volatiles) of the polysiloxane, anyfilm-forming component and any curing agent present during formation ofthe coating composition, but not including the particles, any solvent,or any additive solids such as hindered amine stabilizers, catalysts,photoinitiators, pigments including extender pigments and fillers, flowadditives, and UV light absorbers.

In another embodiment, the present invention is directed to anycomposition as previously described, wherein the at least onepolysiloxane (a) is the reaction product of at least the followingreactants: (i) at least one polysiloxane of the formula (VI):

wherein each substituent group R, which may be identical or different,represents a group selected from H, OH, a monovalent hydrocarbon group,a monovalent siloxane group, and mixtures of any of the foregoing; atleast one of the groups represented by R is H, and n′ ranges from 0 to100, also can range from 0 to 10, and can further range from 0 to 5,such that the percent of SiH content of the polysiloxane ranges from 2to 50 percent, and can range from 5 to 25 percent; and (ii) at least onemolecule which comprises at least one functional group selected ahydroxyl group, a carboxyl group, an isocyanate group, a blockedpolyisocyanate group, a primary amine group, a secondary amine group, anamide group, a carbamate group, a urea group, a urethane group, a vinylgroup, an unsaturated ester group such as an acrylate group and amethacrylate group, a maleimide group, a fumarate group, an onium saltgroup such as a sulfonium group and an ammonium group, an anhydridegroup, a hydroxy alkylamide group, and an epoxy group, and at least oneunsaturated bond capable of undergoing a hydrosilylation reaction. Inanother embodiment, the at least one molecule comprises at least onefunctional group chosen from hydroxyl groups.

It should be appreciated that the various R groups can be the same ordifferent, and, in certain embodiments, the R groups will be entirelymonovalent hydrocarbon groups or will be a mixture of different groupssuch as monovalent hydrocarbon groups and hydroxyl groups.

In another embodiment, this reaction product is ungelled. As usedherein, “ungelled” refers to a reaction product that is substantiallyfree of crosslinking and has an intrinsic viscosity when dissolved in asuitable solvent, as determined, for example, in accordance withASTM-D1795 or ASTM-D4243. The intrinsic viscosity of the reactionproduct is an indication of its molecular weight. A gelled reactionproduct, on the other hand, since it is of an extremely high molecularweight, will have an intrinsic viscosity too high to measure. As usedherein, a reaction product that is “substantially free of crosslinking”refers to a reaction product that has a weight average molecular weight(Mw), as determined by gel permeation chromatography, of less than1,000,000.

It also should be noted that the level of unsaturation contained inreactant (ii) above, can be selected to obtain an ungelled reactionproduct. In other words, when a polysiloxane containing silicon hydride(i) having a higher average value of Si—H functionality is used,reactant (ii) can have a lower level of unsaturation. For example, thepolysiloxane containing silicon hydride (i) can be a low molecularweight material where n′ ranges from 0 to 5 and the average value ofSi—H functionality is two or less. In this case, reactant (ii) cancontain two or more unsaturated bonds capable of undergoinghydrosilylation reaction without the occurrence of gelation.

Nonlimiting examples of polysiloxanes containing silicon hydride (i)include 1,1,3,3-tetramethyl disiloxane where n′ is 0 and the averageSi—H functionality is two; and polymethyl polysiloxane containingsilicon hydride, where n′ ranges from 4 to 5 and the average Si—Hfunctionality is approximately two, such as is commercially availablefrom BASF Corporation as MASILWAX BASE@.

Materials for use as reactant (ii) above can include hydroxyl functionalgroup-containing allyl ethers such as those selected fromtrimethylolpropane monoallyl ether, pentaerythritol monoallyl ether,trimethylolpropane diallyl ether, polyoxyalkylene alcohols such aspolyethoxylated alcohol, polypropoxylated alcohol, and polybutoxylatedalcohol, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylicacid adducts, and mixtures of any of the foregoing. Mixtures of hydroxylfunctional polyallyl ethers with hydroxyl functional monoallyl ethers orallyl alcohols are suitable as well. In certain instances, reactant (ii)can contain at least one unsaturated bond in a terminal position.Reaction conditions and the ratio of reactants (i) and (ii) are selectedso as to form the desired functional group.

The hydroxyl functional group-containing polysiloxane (a) can beprepared by reacting a polysiloxane containing hydroxyl functionalgroups with an anhydride to form the half-ester acid group underreaction conditions that favor only the reaction of the anhydride andthe hydroxyl functional groups, and avoid further esterification fromoccuring. Nonlimiting examples of suitable anhydrides includehexahydrophthalic anhydride, methyl hexahydrophthalic anhydride,phthalic anhydride, trimellitic anhydride, succinic anhydride,chlorendic anhydride, alkenyl succinic anhydride, and substitutedalkenyl anhydrides such as octenyl succinic anhydride, and mixtures ofany of the foregoing.

The half-ester group-containing reaction product thus prepared can befurther reacted with a monoepoxide to form a polysiloxane containingsecondary hydroxyl group(s). Nonlimiting examples of suitablemonoepoxides are phenyl glycidyl ether, n-butyl glycidyl ether, cresylglycidyl ether, isopropyl glycidyl ether, glycidyl versatate, forexample, CARDURA E available from Shell Chemical Co., and mixtures ofany of the foregoing.

In another embodiment, the present invention is directed to compositionsas previously described wherein the at least one polysiloxane (a) is acarbamate functional group-containing polysiloxane which comprises thereaction product of at least the following reactants:

(i) at least one polysiloxane containing silicon hydride of structure(VI) above where R and n′ are as described above for that structure;

(ii) at least one hydroxyl functional group-containing material havingone or more unsaturated bonds capable of undergoing hydrosilylationreaction as described above; and

(iii) at least one low molecular weight carbamate functional material,comprising the reaction product of an alcohol or glycol ether and aurea.

Examples of such “low molecular weight carbamate functional material”include, but are not limited to, alkyl carbamates such as methylcarbamate and hexyl carbamates, and glycol ether carbamates such asthose described in U.S. Pat. Nos. 5,922,475 and 5,976,701, which areincorporated herein by reference.

The carbamate functional groups can be incorporated into thepolysiloxane by reacting the hydroxyl functional group-containingpolysiloxane with the low molecular weight carbamate functional materialvia a “transcarbamoylation” process. The low molecular weight carbamatefunctional material, which can be derived from an alcohol or glycolether, can react with free hydroxyl groups of a polysiloxane polyol,that is, material having an average of two or more hydroxyl groups permolecule, yielding a carbamate functional polysiloxane (a) and theoriginal alcohol or glycol ether. Reaction conditions and the ratio ofreactants (i), (ii) and (iii) are selected so as to form the desiredgroups.

The low molecular weight carbamate functional material can be preparedby reacting the alcohol or glycol ether with urea in the presence of acatalyst such as butyl stannoic acid. Nonlimiting examples of suitablealcohols include lower molecular weight aliphatic, cycloaliphatic andaromatic alcohols, for example, methanol, ethanol, propanol, butanol,cyclohexanol, 2-ethylhexanol, and 3-methylbutanol. Nonlimiting examplesof suitable glycol ethers include ethylene glycol methyl ether, andpropylene glycol methyl ether. The incorporation of carbamate functionalgroups into the polysiloxane also can be achieved by reacting isocyanicacid with free hydroxyl groups of the polysiloxane.

As aforementioned, in addition to or in lieu of hydroxyl or carbamatefunctional groups, the at least one polysiloxane (a) can contain one ormore other reactive functional groups such as carboxyl groups,isocyanate groups, blocked polyisocyanate groups, carboxylate groups,primary or secondary amine groups, amide groups, urea groups, urethanegroups, anhydride groups, hydroxy alkylamide groups, epoxy groups, andmixtures of any of the foregoing.

When at least one polysiloxane (a) contains carboxyl functional groups,the at least one polysiloxane (a) can be prepared by reacting at leastone polysiloxane containing hydroxyl functional groups as describedabove with a polycarboxylic acid or anhydride. Nonlimiting examples ofpolycarboxylic acids suitable for use include adipic acid, succinicacid, and dodecanedioic acid. Nonlimiting examples of suitableanhydrides include those described above. Reaction conditions and theratio of reactants are selected so as to form the desired functionalgroups.

In the case where at least one polysiloxane (a) contains one or moreisocyanate functional groups, the at least one polysiloxane (a) can beprepared by reacting at least one polysiloxane containing hydroxylfunctional groups as described above with a polyisocyanate, such as adiisocyanate. Nonlimiting examples of suitable polyisocyanates includealiphatic polyisocyanates, such as aliphatic diisocyanates, for example,1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate;cycloaliphatic polyisocyanates, for example, 1,4-cyclohexyldiisocyanate, isophorone diisocyanate, and α,α-xylylene diisocyanate;and aromatic polyisocyanates, for example, 4,4′-diphenylmethanediisocyanate, 1,3-phenylene diisocyanate, and tolylene diisocyanate.These and other suitable polyisocyanates are described in more detail inU.S. Pat. No. 4,046,729, at column 5, line 26 to column 6, line 28,incorporated herein by reference. Reaction conditions and the ratio ofreactants are selected so as to form the desired functional groups.

The substituent group X in structure (IV) can comprise a polymericurethane or urea-containing material which is terminated withisocyanate, hydroxyl, primary or secondary amine functional groups, ormixtures of any of the foregoing. When the substituent group X comprisessuch functional groups, the at least one polysiloxane (a) can be thereaction product of at least a polysiloxane polyol as described above,one or more polyisocyanates and, optionally, one or more compoundshaving at least two active hydrogen atoms per molecule selected fromhydroxyl groups, primary amine groups, and secondary amine groups.

Nonlimiting examples of suitable polyisocyanates are those describedabove. Nonlimiting examples of compounds having at least two activehydrogen atoms per molecule include polyols and polyamines containingprimary or secondary amine groups.

Nonlimiting examples of suitable polyols include polyalkylene etherpolyols, including thio ethers; polyester polyols, including polyhydroxypolyesteramides; and hydroxyl-containing polycaprolactones andhydroxy-containing acrylic interpolymers. Also useful are polyetherpolyols formed from the oxyalkylation of various polyols, for example,glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and thelike, or higher polyols such as trimethylolpropane, pentaerythritol andthe like. Polyester polyols also can be used. These and other suitablepolyols are described in U.S. Pat. No. 4,046,729 at column 7, line 52 tocolumn 8, line 9; column 8, line 29 to column 9, line 66; and U.S. Pat.No. 3,919,315 at column 2, line 64 to column 3, line 33, bothincorporated herein by reference.

Nonlimiting examples of suitable polyamines include primary or secondarydiamines or polyamines in which the groups attached to the nitrogenatoms can be saturated or unsaturated, aliphatic, alicyclic, aromatic,aromatic-substituted-aliphatic, aliphatic-substituted-aromatic andheterocyclic. Exemplary suitable aliphatic and alicyclic diaminesinclude 1,2-ethylene diamine, 1,2-porphylene diamine, 1,8-octanediamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like.Suitable aromatic diamines include phenylene diamines and the toluenediamines, for example, o-phenylene diamine and p-tolylene diamine. Theseand other suitable polyamines are described in detail in U.S. Pat. No.4,046,729 at column 6, line 61 to column 7, line 26, incorporated hereinby reference.

In one embodiment, the substituent group X of the structure (IV) cancomprise a polymeric ester-containing group which is terminated withhydroxyl or carboxylic acid functional groups. When X is such a group,at least one polysiloxane (a) can be the reaction product of one or morepolysiloxane polyols as described above, one or more materials having atleast one carboxylic acid functional group, and one or more organicpolyols. Nonlimiting suitable examples of materials having at least onecarboxylic acid functional group include carboxylic acidgroup-containing polymers well-known in the art, for example, carboxylicacid group-containing acrylic polymers, polyester polymers, andpolyurethane polymers, such as those described in U.S. Pat. No.4,681,811. Nonlimiting examples of suitable organic polyols includethose described above.

To form the at least one polysiloxane (a) containing epoxy groups, atleast one polysiloxane containing hydroxyl functional groups asdescribed above can be further reacted with a polyepoxide. Thepolyepoxide can be an aliphatic or cycloaliphatic polyepoxide ormixtures of any of the foregoing. Nonlimiting examples of polyepoxidessuitable for use include epoxy functional acrylic copolymers preparedfrom at least one ethylenically unsaturated monomer having at least oneepoxy group, for example glycidyl (meth)acrylate and allyl glycidylether, and one or more ethylenically unsaturated monomers which have noepoxy functionality. The preparation of such epoxy functional acryliccopolymers is described in detail in U.S. Pat. No. 4,681,811 at column4, line 52 to column 5, line 50, incorporated herein by reference.Reaction conditions and the ratio of reactants are selected so as toform the desired functional groups.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the composition comprises a plurality ofparticles. In another embodiment, the present invention is directed tocompositions as previously described wherein the particles have anaverage particle size less than 50 microns prior to incorporation intothe composition. In another embodiment, the present invention isdirected to compositions as previously described wherein the particleshave an average particle size ranging from 1 to less than 1000nanometers prior to incorporation into the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles have an average particle sizeranging from 1 to 100 nanometers prior to incorporation into thecomposition.

In another embodiment, the present invention is directed to compositionsas previously described wherein the particles have an average particlesize ranging from 5 to 50 nanometers prior to incorporation into thecomposition. In another embodiment, the present invention is directed tocompositions as previously described wherein the particles have anaverage particle size ranging from 5 to 25 nanometers prior toincorporation into the composition. The particle size may range betweenany combination of these values inclusive of the recited values.

In an embodiment where the average particle size of the particles isgreater than one micron, the average particle size can be measuredaccording to known laser scattering techniques. For example, the averageparticle size of such particles is measured using a Horiba Model LA 900laser diffraction particle size instrument, which uses a helium-neonlaser with a wave length of 633 nm to measure the size of the particlesand assumes the particle has a spherical shape, i.e., the “particlesize” refers to the smallest sphere that will completely enclose theparticle.

In an embodiment of the present invention wherein the size of theparticles is less than or equal to one micron, the average particle sizecan be determined by visually examining an electron micrograph of atransmission electron microscopy (“TEM”) image, measuring the diameterof the particles in the image, and calculating the average particle sizebased on the magnification of the TEM image. One of ordinary skill inthe art will understand how to prepare such a TEM image, and adescription of one such method is disclosed in the examples set forthbelow. In one nonlimiting embodiment of the present invention, a TEMimage with 105,000× magnification is produced, and a conversion factoris obtained by dividing the magnification by 1000. Upon visualinspection, the diameter of the particles is measured in millimeters,and the measurement is converted to nanometers using the conversionfactor. The diameter of the particle refers to the smallest diametersphere that will completely enclose the particle.

The shape (or morphology) of the particles can vary depending upon thespecific embodiment of the present invention and its intendedapplication. For example generally spherical morphologies (such as solidbeads, microbeads, or hollow spheres), can be used, as well as particlesthat are cubic, platy, or acicular (elongated or fibrous). Additionally,the particles can have an internal structure that is hollow, porous orvoid free, or a combination of any of the foregoing, e.g., a hollowcenter with porous or solid walls. For more information on suitableparticle characteristics see H. Katz et al. (Ed.), Handbook of Fillersand Plastics (1987) at pages 9-10, which are specifically incorporatedby reference herein.

It will be recognized by one skilled in the art that mixtures of one ormore particles having different average particle sizes can beincorporated into the compositions in accordance with the presentinvention to impart the desired properties and characteristics to thecompositions. For example, particles of varying particle sizes can beused in the compositions according to the present invention.

The particles can be formed from materials selected from polymeric andnonpolymeric inorganic materials, polymeric and nonpolymeric organicmaterials, composite materials, and mixtures of any of the foregoing. Asused herein, the term “polymeric inorganic material” means a polymericmaterial having a backbone repeat unit based on an element or elementsother than carbon. For more information see James Mark et al., InorganicPolymers, Prentice Hall Polymer Science and Engineering Series, (1992)at page 5, which is specifically incorporated by reference herein. Asused herein, the term “polymeric organic materials” means syntheticpolymeric materials, semisynthetic polymeric materials and naturalpolymeric materials, all of which have a backbone repeat unit based oncarbon.

An “organic material,” as used herein, means carbon containing compoundswherein the carbon is typically bonded to itself and to hydrogen, andoften to other elements as well, and excludes binary compounds such asthe carbon oxides, the carbides, carbon disulfide, etc.; such ternarycompounds as the metallic cyanides, metallic carbonyls, etc.; andcarbon-containing ionic compounds such as metallic carbonates, forexample, calcium carbonate and sodium carbonate. See R. Lewis, Sr.,Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at pages761-762, and M. Silberberg, Chemistry The Molecular Nature of Matter andChange (1996) at page 586, which are specifically incorporated byreference herein.

As used herein, the term “inorganic material” means any material that isnot an organic material.

As used herein, the term “composite material” means a combination of twoor more differing materials. The particles formed from compositematerials generally have a hardness at their surface that is differentfrom the hardness of the internal portions of the particle beneath itssurface. More specifically, the surface of the particle can be modifiedin any manner well known in the art, including, but not limited to,chemically or physically changing its surface characteristics usingtechniques known in the art.

For example, a particle can be formed from a primary material that iscoated, clad or encapsulated with one or more secondary materials toform a composite particle that has a softer surface. In yet anotheralternative embodiment, particles formed from composite materials can beformed from a primary material that is coated, clad or encapsulated witha different form of the primary material. For more information onparticles useful in the present invention, see G. Wypych, Handbook ofFillers, 2nd Ed. (1999) at pages 15-202, which are specificallyincorporated by reference herein.

The particles suitable for use in the compositions of the invention cancomprise inorganic elements or compounds known in the art. Suitableparticles can be formed from ceramic materials, metallic materials, andmixtures of any of the foregoing. Suitable ceramic materials comprisemetal oxides, metal nitrides, metal carbides, metal sulfides, metalsilicates, metal borides, metal carbonates, and mixtures of any of theforegoing. Specific, nonlimiting examples of metal nitrides are, forexample, boron nitride; specific, nonlimiting examples of metal oxidesare, for example, zinc oxide; nonlimiting examples of suitable metalsulfides are, for example, molybdenum disulfide, tantalum disulfide,tungsten disulfide, and zinc sulfide; nonlimiting suitable examples ofmetal silicates are, for example, aluminum silicates and magnesiumsilicates such as vermiculite.

The particles can comprise, for example, a core of essentially a singleinorganic oxide such as silica in colloidal, fumed, or amorphous form,alumina or colloidal alumina, titanium dioxide, cesium oxide, yttriumoxide, colloidal yttria, zirconia, e.g., colloidal or amorphouszirconia, and mixtures of any of the foregoing; or an inorganic oxide ofone type upon which is deposited an organic oxide of another type. Itshould be understood that when the composition of the invention isemployed as a transparent topcoat, for example, as a clearcoat in amulti-component composite coating composition, particles should notseriously interfere with the optical properties of the composition. Asused herein, “transparent” means that the cured coating has a BYK Hazeindex of less than 50 as measured using a BYK/Haze Gloss instrument.

Nonpolymeric, inorganic materials useful in forming the particles of thepresent invention comprise inorganic materials selected from graphite,metals, oxides, carbides, nitrides, borides, sulfides, silicates,carbonates, sulfates, and hydroxides. A nonlimiting example of a usefulinorganic oxide is zinc oxide. Nonlimiting examples of suitableinorganic sulfides include molybdenum disulfide, tantalum disulfide,tungsten disulfide, and zinc sulfide. Nonlimiting examples of usefulinorganic silicates include aluminum silicates and magnesium silicates,such as vermiculite. Nonlimiting examples of suitable metals includemolybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron,silver, alloys, and mixtures of any of the foregoing.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the particles are selected from fumedsilica, amorphous silica, colloidal silica, alumina, colloidal alumina,titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria,zirconia, colloidal zirconia, and mixtures of any of the foregoing. Inanother embodiment, the present invention is directed to compositions aspreviously described wherein the particles include colloidal silica. Asdisclosed above, these materials can be surface treated or untreated.

The composition can comprise precursors suitable for forming silicaparticles in situ by a sol-gel process. The composition according to thepresent invention can comprise alkoxy silanes which can be hydrolyzed toform silica particles in situ. For example, tetraethylortho silicate canbe hydrolyzed with an acid such as hydrochloric acid and condensed toform silica particles. Other useful particles include surface-modifiedsilicas such as are described in U.S. Pat. No. 5,853,809 at column 6,line 51 to column 8, line 43, which is incorporated herein by reference.

In one embodiment of the present invention, the particles have ahardness value greater than the hardness value of materials that canabrade a polymeric coating or a polymeric substrate. Examples ofmaterials that can abrade the polymeric coating or polymeric substrateinclude, but are not limited to, dirt, sand, rocks, glass, carwashbrushes, and the like. The hardness values of the particles and thematerials that can abrade the polymeric coating or polymeric substratecan be determined by any conventional hardness measurement method, suchas Vickers or Brinell hardness, but is preferably determined accordingto the original Mohs' hardness scale which indicates the relativescratch resistance of the surface of a material on a scale of one toten. The Mohs' hardness values of several nonlimiting examples ofparticles formed from inorganic materials suitable for use in thepresent invention are given in Table A below.

TABLE A Particle material Mohs' hardness (original scale) Boron nitride2¹ Graphite 0.5-1² Molybdenum disulfide 1³ Talc 1-1.5⁴ Mica 2.8-3.2⁵Kaolinite 2.0-2.56 Gypsum 1.6-2⁷ Calcite (calcium carbonate) 3⁸ Calciumfluoride 4⁹ zinc oxide 4.5¹⁰ Aluminum 2.5¹¹ Copper 2.5-3¹² Iron 4-5¹³Gold 2.5-3¹⁴ Nickel 5¹⁵ Palladium 4.8¹⁶ Platinum 4.3¹⁷ Silver 2.5-4¹⁸Zinc sulfide 3.5-4¹⁹ ¹K. Ludema, Friction, Wear, Lubrication, (1996) atpage 27, which is hereby incorporated by reference. ²R. Weast (Ed.),Handbook of Chemistry and Physics, CRC Press (1975) at page F-22. ³R.Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) atpage 793, which is hereby incorporated by reference. ⁴Hawley's CondensedChemical Dictionary, (12th Ed. 1993) at page 1113, which is herebyincorporated by reference. ⁵Hawley's Condensed Chemical Dictionary,(12th Ed. 1993) at page 784, which is hereby incorporated by reference.⁶Handbook of Chemistry and Physics at page F-22. ⁷Handbook of Chemistryand Physics at page F-22. ⁸Friction, Wear, Lubrication at page 27.⁹Friction, Wear, Lubrication at page 27. ¹⁰Friction, Wear, Lubricationat page 27. ¹¹Friction, Wear, Lubrication at page 27. ¹² Handbook ofChemistry and Physics at page F-22. ¹³Handbook of Chemistry and Physicsat page F-22. ¹⁴Handbook of Chemistry and Physics at page F-22.¹⁵Handbook of Chemistry and Physics at page F-22. ¹⁶Handbook ofChemistry and Physics at page F-22. ¹⁷Handbook of Chemistry and Physicsat page F-22. ¹⁸Handbook of Chemistry and Physics at page F-22. ¹⁹R.Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (71^(st) Ed.1990) at page 4-158.

In one embodiment, the Mohs' hardness value of the particles is greaterthan 5. In certain embodiments, the Mohs' hardness value of theparticles, such as silica, is greater than 6.

As mentioned above, the Mohs' hardness scale relates to the resistanceof a material to scratching. The present invention therefore furthercontemplates particles that have a hardness at their surface that isdifferent from the hardness of the internal portions of the particlebeneath its surface. More specifically, and as discussed above, thesurface of the particle can be modified in any manner well known in theart, including, but not limited to, chemically changing the particle'ssurface characteristics using techniques known in the art such that thesurface hardness of the particle is greater the hardness of thematerials that can abrade the polymeric coating or polymeric substratewhile the hardness of the particle beneath the surface is less than thehardness of the materials that can abrade the polymeric coating orpolymeric substrate.

As another alternative, a particle can be formed from a primary materialthat is coated, clad or encapsulated with one or more secondarymaterials to form a composite material that has a harder surface.Alternatively, a particle can be formed from a primary material that iscoated, clad or encapsulated with a differing form of the primarymaterial to form a composite material that has a harder surface.

In one example, and without limiting the present invention, an inorganicparticle formed from an inorganic material such as silicon carbide oraluminum nitride can be provided with a silica, carbonate or nanoclaycoating to form a useful composite particle. In another nonlimitingexample, a silane coupling agent with alkyl side chains can interactwith the surface of an inorganic particle formed from an inorganic oxideto provide a useful composite particle having a “softer” surface. Otherexamples include cladding, encapsulating or coating particles formedfrom nonpolymeric or polymeric materials with differing nonpolymeric orpolymeric materials. A specific nonlimiting example of such compositeparticles is DUALITE™, which is a synthetic polymeric particle coatedwith calcium carbonate that is commercially available from Pierce andStevens Corporation of Buffalo, N.Y.

In one nonlimiting embodiment of the invention, the particles are formedfrom solid lubricant materials. As used herein, the term “solidlubricant” means any solid used between two surfaces to provideprotection from damage during relative movement or to reduce frictionand wear. In one embodiment, the solid lubricants are inorganic solidlubricants. As used herein, “inorganic solid lubricant” means that thesolid lubricants have a characteristic crystalline habit which causesthem to shear into thin, flat plates which readily slide over oneanother and thus produce an antifriction lubricating effect. See R.Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) atpage 712, which is specifically incorporated by reference herein.Friction is the resistance to sliding one solid over another. F. Clauss,Solid Lubricants and Self-Lubricating Solids (1972) at page 1, which isspecifically incorporated by reference herein.

In one nonlimiting embodiment of the invention, the particles have alamellar structure. Particles having a lamellar structure are composedof sheets or plates of atoms in hexagonal array, with strong bondingwithin the sheet and weak van der Waals bonding between sheets,providing low shear strength between sheets. A nonlimiting example of alamellar structure is a hexagonal crystal structure. Inorganic solidparticles having a lamellar fullerene (i.e., buckyball) structure alsoare useful in the present invention.

Nonlimiting examples of suitable materials having a lamellar structurethat are useful in forming the particles of the present inventioninclude boron nitride, graphite, metal dichalcogenides, mica, talc,gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixturesof any of the foregoing. Suitable metal dichalcogenides includemolybdenum disulfide, molybdenum diselenide, tantalum disulfide,tantalum diselenide, tungsten disulfide, tungsten diselenide, andmixtures of any of the foregoing.

The particles can be formed from nonpolymeric, organic materials.Nonlimiting examples of nonpolymeric, organic materials useful in thepresent invention include, but are not limited to, stearates (such aszinc stearate and aluminum stearate), diamond, carbon black, andstearamide.

The particles can be formed from inorganic polymeric materials.Nonlimiting examples of useful inorganic polymeric materials includepolyphosphazenes, polysilanes, polysiloxane, polygeremanes, polymericsulfur, polymeric selenium, silicones, and mixtures of any of theforegoing. A specific, nonlimiting example of a particle formed from aninorganic polymeric material suitable for use in the present inventionis TOSPEARL ²⁰, which is a particle formed from cross-linked siloxanesand is commercially available from Toshiba Silicones Company, Ltd. ofJapan.

²⁰ See R. J. Perry “Applications for Cross-Linked Siloxane Particles”Chemtech, February 1999 at pages 39-44.

The particles can be formed from synthetic, organic polymeric materials.Nonlimiting examples of suitable organic polymeric materials include,but are not limited to, thermoset materials and thermoplastic materials.As used herein, a “thermoplastic” material is a material that softenswhen exposed to heat and returns to its original condition when cooledto room temperature. Nonlimiting examples of suitable thermoplasticmaterials include thermoplastic polyesters such as polyethyleneterephthalate, polybutylene terephthalate, and polyethylene naphthalate,polycarbonates, polyolefins such as polyethylene, polypropylene, andpolyisobutene, acrylic polymers such as copolymers of styrene and anacrylic acid monomer, and polymers containing methacrylate, polyamides,thermoplastic polyurethanes, vinyl polymers, and mixtures of any of theforegoing.

Nonlimiting examples of suitable thermoset materials include thermosetpolyesters, vinyl esters, epoxy materials, phenolics, aminoplasts,thermoset polyurethanes, and mixtures of any of the foregoing. Aspecific, nonlimiting example of a synthetic polymeric particle formedfrom an epoxy material is an epoxy microgel particle. As used herein, a“thermoset” material is a material that solidifies or “sets”irreversibly when heated. A thermoset material has formed a crosslinkednetwork. As used herein, a polymeric material is “crosslinked” if it atleast partially forms a polymeric network. One skilled in the art willunderstand that the presence and degree of crosslinking (crosslinkdensity) can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA) using a TA Instruments DMA 2980 DMTAanalyzer conducted under nitrogen. This method determines the glasstransition temperature and crosslink density of free films of coatingsor polymers. These physical properties of a cured material are relatedto the structure of the crosslinked network.

The particles also can be hollow particles formed from materialsselected from polymeric and nonpolymeric inorganic materials, polymericand nonpolymeric organic materials, composite materials, and mixtures ofany of the foregoing. Nonlimiting examples of suitable materials fromwhich the hollow particles can be formed are described above.

In an embodiment of the present invention, the at least one polysiloxane(a) is nonreactive with the particles.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount ranging from 0.01 to 75 weight percent based on total weight ofthe resin solids of the components which form the composition. Inanother embodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount of at least 0.1 weight percent based on total weight of the resinsolids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount greater than 0.5 weight percent based on total weight of theresin solids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount greater than 5 weight percent based on total weight of the resinsolids of the components which form the composition.

In yet another embodiment, the present invention is directed tocompositions as previously described wherein, the particles, when addedto the other components of the composition, are present in thecomposition in an amount less than 75 weight percent based on totalweight of the resin solids of the components which form the composition.In a further embodiment, the present invention is directed tocompositions as previously described wherein the particles, when addedto the other components of the composition, are present in thecomposition in an amount less than 50 weight percent based on totalweight of the resin solids of the components which form the composition.In another embodiment, the present invention is directed to compositionsas previously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount less than 20 weight percent based on total weight of the resinsolids of the components which form the composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the particles, when added to the othercomponents of the composition, are present in the composition in anamount less than 10 weight percent based on total weight of the resinsolids of the components which form the composition. The amount ofparticles may range betweeen any combination of these values inclusiveof the recited values.

Prior to incorporation, one class of particles which can be usedaccording to the present invention includes sols, such as an organosol,of the particles. These sols can be of a wide variety of small-particle,colloidal silicas having an average particle size in ranges such asidentified above.

The colloidal silicas can be surface modified during or after theparticles are initially formed. These surface modified silicas maycontain on their surface chemically bonded carbon-containing moieties,as well as such groups as anhydrous SiO₂ groups and SiOH groups, variousionic groups physically associated or chemically bonded within thesurface of the silica, adsorbed organic groups, or combinations of anyof the foregoing, depending on the characteristics of the particularsilica desired. Such surface modified silicas are described in detail inU.S. Pat. No. 4,680,204, which is incorporated herein by reference.

Such materials can be prepared by a variety of techniques in variousforms, nonlimiting examples comprise organosols and mixed sols. As usedherein the term “mixed sols” is intended to include those dispersions ofcolloidal silica in which the dispersing medium comprises both anorganic liquid and water. Such small particle colloidal silicas arereadily available, are essentially colorless and have refractive indiceswhich permit their inclusion in compositions that, without additionalpigments or components known in the art to color or decrease thetransparency of such compositions, result in colorless, transparentcoatings.

Suitable nonlimiting examples of particles include colloidal silicas,such as those commercially available from Nissan Chemical Company underthe trademark ORGANOSILICASOLS™ such as ORGANOSILICASOL™ MT-ST, and fromClariant Corporation as HIGHLINK™; colloidal aluminas, such as thosecommercially available from Nalco Chemical under the trademark NALCO8676®; and colloidal zirconias, such as those commercially availablefrom Nissan Chemical Company under the trademark HIT-32M®.

The particles can be incorporated into the compositions of the inventionin the form of a stable dispersion. When the particles are in acolloidal form, the dispersions can be prepared by dispersing theparticles in a carrier under agitation and solvent that is present canbe removed under vacuum at ambient temperatures. In certain embodiments,the carrier can be other than a solvent, such as the surface activeagents described in detail below, including, but not limited to apolysiloxane containing reactive functional groups, including, but notlimited to, the at least one polysiloxane (a).

In one embodiment, the particles, such as colloidal silica, aredispersed in the at least one polysiloxane (a). Alternatively, thedispersions can be prepared as described in U.S. Pat. Nos. 4,522,958 or4,526,910, which are incorporated by reference herein. The particles canbe “cold-blended” with the at least one polysiloxane (a) prior toincorporation into, the inventive compositions. Alternatively, theparticles can be post-added to an admixture of any remaining compositioncomponents (including, but not limited to, the at least one polysiloxane(a)) and dispersed therein using dispersing techniques well-known in theart.

When the particles are in other than colloidal form, for example, butnot limited to, agglomerate form, the dispersions can be prepared bydispersing the agglomerate in the carrier, for example, but not limitedto, the at least one polysiloxane (a), to stably disperse the particlestherein. Dispersion techniques such as grinding, milling,microfluidizing, ultrasounding, or any other pigment dispersingtechniques well known in the art of coatings formulation can be used.Alternatively, the particles can be dispersed by any other dispersiontechniques known in the art. If desired, the particles in other thancolloidal form can be post-added to an admixture of other compositioncomponents and dispersed therein using any dispersing techniques knownin the art.

The particles according to the present invention that are applied to thepolymeric substrate or polymeric coating, for example, but not limitedto, the electrodeposited coating, the primer coating, or the topcoat,can be present in a dispersion, suspension or emulsion in a carrier.Nonlimiting examples of suitable carriers include, but are not limitedto, water, solvents, surfactants, or a mixture of any of the foregoing.Nonlimiting examples of suitable solvents include, but are not limitedto, mineral oil, alcohols such as methanol or butanol, ketones such asmethyl amyl ketone, aromatic hydrocarbons such as xylene, glycol etherssuch as ethylene glycol monobutyl ether, esters, aliphatics, andmixtures of any of the foregoing.

As discussed above, besides the at least one polysiloxane (a), thecompositions of the present invention can be formed from at least onereactant comprising at least one functional group that is reactive withat least one reactive functional group of the at least one polysiloxane(a). In one embodiment, the at least one reactant is selected from atleast one curing agent.

In a further embodiment, the present invention is directed tocompositions as previously described wherein a curing agent is present.This curing agent can be selected from an aminoplast resin, apolyisocyanate, a blocked polyisocyanate, a polyepoxide, a polyacid, apolyol, and mixtures of any of the foregoing.

In another embodiment, the present invention is directed to compositionsas previously described wherein the curing agent is an aminoplast.Aminoplast resins, which comprise phenoplasts, as curing agents forhydroxyl, carboxylic acid, and carbamate functional group-containingmaterials are well known in the art. Suitable aminoplasts, such as thosediscussed above, are known to those of ordinary skill in the art.Aminoplasts can be obtained from the condensation reaction offormaldehyde with an amine or amide. Nonlimiting examples of amines oramides include melamine, urea, or benzoguanamine. Condensates with otheramines or amides can be used; for example, aldehyde condensates ofglycoluril, which give a high melting crystalline product useful inpowder coatings. While the aldehyde used is most often formaldehyde,other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehydecan be used.

The aminoplast contains imino and methylol groups and in certaininstances at least a portion of the methylol groups are etherified withan alcohol to modify the cure response. Any monohydric alcohol can beemployed for this purpose including methanol, ethanol, n-butyl alcohol,isobutanol, and hexanol.

Nonlimiting examples of aminoplasts include melamine-, urea-, orbenzoguanamine-formaldehyde condensates, in certain instances monomericand at least partially etherified with one or more alcohols containingfrom one to four carbon atoms. Nonlimiting examples of suitableaminoplast resins are commercially available, for example, from CytecIndustries, Inc. under the trademark CYMEL®, and from Solutia, Inc.under the trademark RESIMENE®.

In another embodiment, the present invention is directed to compositionsas previously described wherein the curing agent, when added to theother components of the composition, is generally present in an amountranging from 1 weight percent to 65 weight percent based on total weightof the resin solids of the components which form the composition.

Other curing agents suitable for use include, but are not limited to,polyisocyanate curing agents. As used herein, the term “polyisocyanate”is intended to include blocked (or capped) polyisocyanates as well asunblocked polyisocyanates. The polyisocyanate can be an aliphatic or anaromatic polyisocyanate, or a mixture of the foregoing two.Diisocyanates can be used, although higher polyisocyanates such asisocyanurates of diisocyanates are often used. Higher polyisocyanatesalso can be used in combination with diisocyanates. Isocyanateprepolymers, for example, reaction products of polyisocyanates withpolyols also can be used. Mixtures of polyisocyanate curing agents canbe used.

If the polyisocyanate is blocked or capped, any suitable aliphatic,cycloaliphatic, or aromatic alkyl monoalcohol known to those skilled inthe art can be used as a capping agent for the polyisocyanate. Othersuitable capping agents include oximes and lactams. When used, thepolyisocyanate curing agent is typically present, when added to theother components in the composition, in an amount ranging from 5 to 65weight percent, can be present in an amount ranging from 10 to 45 weightpercent, and often are present in an amount ranging from 15 to 40percent by weight based on the total weight of the resin solids of thecomponents which form the composition, inclusive of the recited values.

Other useful curing agents comprise blocked isocyanate compounds such asthe tricarbamoyl triazine compounds described in detail in U.S. Pat. No.5,084,541, which is incorporated by reference herein. When used, theblocked isocyanate curing agent can be present, when added to the othercomponents in the composition, in an amount ranging up to 20 weightpercent, and can be present in an amount ranging from 1 to 20 weightpercent, based on the total weight of the resin solids of the componentswhich form the composition, inclusive of the recited values.

Anhydrides as curing agents for hydroxyl functional group-containingmaterials also are well known in the art and can be used in the presentinvention. Nonlimiting examples of anhydrides suitable for use as curingagents in the compositions of the invention include those having atleast two carboxylic acid anhydride groups per molecule which arederived from a mixture of monomers comprising an ethylenicallyunsaturated carboxylic acid anhydride and at least one vinyl co-monomer,for example, styrene, alpha-methyl styrene, vinyl toluene, and the like.Nonlimiting examples of suitable ethylenically unsaturated carboxylicacid anhydrides include maleic anhydride, citraconic anhydride, anditaconic anhydride. Alternatively, the anhydride can be an anhydrideadduct of a diene polymer such as maleinized polybutadiene or amaleinized copolymer of butadiene, for example, a butadiene/styrenecopolymer. These and other suitable anhydride curing agents aredescribed in U.S. Pat. No. 4,798,746 at column 10, lines 16-50; and inU.S. Pat. No. 4,732,790 at column 3, lines 41-57, both of which areincorporated herein by reference.

Polyepoxides as curing agents for carboxylic acid functionalgroup-containing materials are well known in the art. Nonlimitingexamples of polyepoxides suitable for use in the compositions of thepresent invention comprise polyglycidyl ethers of polyhydric phenols andof aliphatic alcohols, which can be prepared by etherification of thepolyhydric phenol, or aliphatic alcohol with an epihalohydrin such asepichlorohydrin in the presence of alkali. These and other suitablepolyepoxides are described in U.S. Pat. No. 4,681,811 at column 5, lines33 to 58, which is incorporated herein by reference.

Suitable curing agents for epoxy functional group-containing materialscomprise polyacid curing agents, such as the acid group-containingacrylic polymers prepared from an ethylenically unsaturated monomercontaining at least one carboxylic acid group and at least oneethylenically unsaturated monomer which is free from carboxylic acidgroups. Such acid functional acrylic polymers can have an acid numberranging from 30 to 150. Acid functional group-containing polyesters canbe used as well. The above-described polyacid curing agents aredescribed in further detail in U.S. Pat. No. 4,681,811 at column 6, line45 to column 9, line 54, which is incorporated herein by reference.

Also well known in the art as curing agents for isocyanate functionalgroup-containing materials are polyols, that is, materials having two ormore hydroxyl groups per molecule. Nonlimiting examples of suchmaterials suitable for use in the compositions of the invention includepolyalkylene ether polyols, including thio ethers; polyester polyols,including polyhydroxy polyesteramides; and hydroxyl-containingpolycaprolactones and hydroxy-containing acrylic interpolymers. Alsouseful are polyether polyols formed from the oxyalkylation of variouspolyols, for example, glycols such as ethylene glycol, 1,6-hexanediol,Bisphenol A and the like, or higher polyols such as trimethylolpropane,pentaerythritol, and the like. Polyester polyols also can be used. Theseand other suitable polyol curing agents are described in U.S. Pat. No.4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 tocolumn 9, line 66; and U.S. Pat. No. 3,919,315 at column 2, line 64 tocolumn 3, line 33, both of which are incorporated herein by reference.

Polyamines also can be used as curing agents for isocyanate functionalgroup-containing materials. Nonlimiting examples of suitable polyaminecuring agents include primary or secondary diamines or polyamines inwhich the radicals attached to the nitrogen atoms can be saturated orunsaturated, aliphatic, alicyclic, aromatic,aromatic-substituted-aliphatic, aliphatic-substituted aromatic, andheterocyclic. Nonlimiting examples of suitable aliphatic and alicyclicdiamines include 1,2-ethylene diamine, 1,2-porphylene diamine,1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine,and the like. Nonlimiting examples of suitable aromatic diamines includephenylene diamines and the toluene diamines, for example, o-phenylenediamine and p-tolylene diamine. These and other suitable polyaminesdescribed in detail in U.S. Pat. No. 4,046,729 at column 6, line 61 tocolumn 7, line 26, which is incorporated herein by reference.

When desired, appropriate mixtures of curing agents may be used. Itshould be mentioned that compositions can be formulated as aone-component composition where a curing agent such as an aminoplastresin and/or a blocked polyisocyanate such as those described above isadmixed with other composition components. The one-component compositioncan be storage stable as formulated. Alternatively, compositions can beformulated as a two-component composition where a polyisocyanate curingagent such as those described above can be added to a pre-formedadmixture of the other composition components just prior to application.The pre-formed admixture can comprise curing agents such as aminoplastresins and/or triazine compounds such as those described above.

In another embodiment in which the coating is cured by actinic radiationor the combination of actinic radiation and thermal energy, thecomponents from which the coating composition are formed further cancomprise at least one photoinitiator or photosensitizer which providesfree radicals or cations to initiate the polymerization process. Usefulphotoinitiators have an adsorption in the range of 150 to 2,000 nm.Non-limiting examples of useful photoinitiators include benzoin,benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone,substituted benzoins such as butyl isomers of benzoin ethers,α,α-diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone,2-hydroxy-2-methyl-1-phenyl propane 1-one and 2,4,6-trimethyl benzoyldiphenyl phosphine oxide.

In an alternative embodiment, the reactant can comprise at least onematerial which has at least one reactive functional group which isblocked with a silyl group. This silyl-blocked material is differentfrom the polysiloxane (a) discussed above. Hydrolysis of the silyl groupregenerates the reactive functional group on the material which isavailable for further reaction with the curing agent. A non-limitingexample of suitable silyl blocking groups include those having thefollowing structure (IX):

wherein each R₁, R₂ and R₃, which may be identical or different,represents an alkyl group having from 1 to 18 carbon atoms, a phenylgroup or an allyl group.

Non-limiting examples of suitable functional groups which can be blockedby the silyl group comprise hydroxyl groups, carbamate groups, carboxylgroups, amide groups and mixtures thereof. In one embodiment, thefunctional groups are hydroxyl groups.

Non-limiting examples of suitable compounds which can be reacted withthe functional group to form the silyl group comprisehexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine,t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride,hexamethyl disilylazide, hexamethyl disiloxane, trimethylsilyl triflate,hexamethyldisilyl acetamide, N,N′-bis[trimethylsilyl]-urea, and mixturesof any of the foregoing.

Further examples of suitable compounds for silylation reactions, andsuitable reaction conditions and reagents for trimethylsilylationreactions are discussed in Example 28 below and in T. Greene et al.,Protective Groups in Organic Synthesis, (2d. ed. 1991) at pages 68-86and 261-263, which are incorporated herein by reference.

The backbone of the material can be a compound which comprises at leastone linkage selected from an ester linkage, a urethane linkage, a urealinkage, an amide linkage, a siloxane linkage, and an ether linkage or apolymer such as a polyester, an acrylic polymer, a polyurethane, apolyether, a polyurea, a polyamide, and copolymers of any of theforegoing.

Suitable compounds or polymers having at least one ester linkage and atleast one reactive functional group include half-esters formed fromreacting at least one polyol with at least one 1,2-anhydride. Thehalf-esters are suitable because they are of relatively low molecularweight and are quite reactive with epoxy functionality.

The half-ester is obtained, for example, by reaction between a polyoland a 1,2-anhydride under conditions sufficient to ring open theanhydride forming the half-ester with substantially nopolyesterification occurring. Such reaction products are of relativelylow molecular weight with narrow molecular weight distributions and lowviscosity. By “substantially no polyesterification occurring” means thatthe carboxyl groups formed by the reaction of the anhydride are notfurther esterified by the polyol in a recurring manner. Further to thisembodiment less than 10, and typically less than 5 weight percent ofhigh molecular weight polyester is formed based on the resin solids ofthe components which form the coating composition.

The 1,2-anhydride and polyol can be mixed together and the reaction canbe conducted in the presence of an inert atmosphere such as nitrogen anda solvent such as a ketone or aromatic hydrocarbon to dissolve the solidingredients and/or lower the viscosity of the reaction mixture.

In one embodiment, for the desired ring opening reaction and half-esterformation, a 1,2-dicarboxylic anhydride can be used. Reaction of apolyol with a carboxylic acid instead of an anhydride would requireesterification by condensation and elimination of water by distillation,and such conditions would promote undesired polyesterification.According to the present invention, the reaction temperature can be low,i.e., less than 135° C. and typically ranging from 70° C. to 135° C. Thetime of reaction can vary somewhat depending upon the temperature ofreaction, and generally ranges from 10 minutes to 24 hours.

The equivalent ratio of anhydride to hydroxyl on the polyol can be atleast 0.8:1 (the anhydride being considered monofunctional) to obtainmaximum conversion to the desired half-ester. Ratios less than 0.8:1 canbe used but such ratios may result in increased formation of lowerfunctionality half-esters.

Useful anhydrides include aliphatic, cycloaliphatic, olefinic,cycloolefinic and aromatic anhydrides. Substituted aliphatic andaromatic anhydrides also are useful provided the substituents do notadversely affect the reactivity of the anhydride or the properties ofthe resultant polyester. Examples of substituents include chloro, alkyland alkoxy. Examples of anhydrides include succinic anhydride,methylsuccinic anhydride, dodecenyl succinic anhydride,octadecenylsuccinic anhydride, phthalic anhydride, tetrahydrophthalicanhydride, methyltetrahydrophthalic anhydride, hexahydrophthalicanhydride, alkyl hexahydrophthalic anhydrides such asmethylhexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylene tetrahydrophthalic anhydride, chlorendic anhydride,itaconic anhydride, citraconic anhydride and maleic anhydride.

Among the polyols which can be used are simple polyols, that is, thosecontaining from 2 to 20 carbon atoms, as well as polymeric polyols suchas polyester polyols, polyurethane polyols and acrylic polyols.

Among the simple polyols which can be used are diols, triols, tetrolsand mixtures thereof. Non-limiting examples of the polyols include thosecontaining from 2 to 10 carbon atoms such as aliphatic polyols. Specificexamples include but are not limited to the following compositions:di-trimethylol propane (bis(2,2-dimethylol)dibutylether);pentaerythritol; 1,2,3,4-butanetetrol; sorbitol; trimethylolpropane;trimethylolethane; 1,2,6-hexanetriol; glycerine; trishydroxyethylisocyanurate; dimethylol propionic acid; 1,2,4-butanetriol;2-ethyl-1,3-hexanediol; TMP/epsilon-caprolactone triols; ethyleneglycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol;1,5-pentanediol; 1,6-hexanediol; neopentyl glycol; diethylene glycol;dipropylene glycol; 1,4-cyclohexanedimethanol and2,2,4-trimethylpentane-1,3 diol.

With regard to oligomeric polyols, suitable polyols which can be usedare polyols made from reaction of diacids with triols, such astrimethylol propane/cyclohexane diacid and trimethylol propane/adipicacid.

With regard to polymeric polyols, the polyester polyols can be preparedby esterification of an organic polycarboxylic acid or anhydride thereofwith organic polyols and/or an epoxide. Usually, the polycarboxylicacids and polyols are aliphatic or aromatic dibasic acids or acidanhydrides and diols.

The polyols which can be employed in making the polyester includetrimethylol propane, di-trimethylol propane, alkylene glycols such asethylene glycol, neopentyl glycol and other glycols such as hydrogenatedbisphenol A, cyclohexanediol, cyclohexanedimethanol, the reactionproducts of lactones and diols, for example, the reaction product ofepsilon-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols,polyester glycols, for example, poly(oxytetramethylene)glycol and thelike.

The acid component of the polyester comprises monomeric carboxylic acidsor anhydrides having 2 to 18 carbon atoms per molecule. Among the acidswhich which can be used are phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,methylhexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid,maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acidand other dicarboxylic acids of varying types. Also, there may beemployed higher polycarboxylic acids such as trimellitic acid andtricarballylic acid.

Besides the polyester polyols formed from polybasic acids and polyols,polylactone-type polyesters also can be employed. These products can beformed from the reaction of a lactone such as epsilon-caprolactone and apolyol such as ethylene glycol, diethylene glycol andtrimethylolpropane.

Besides polyester polyols, polyurethane polyols such aspolyester-urethane polyols which can be formed from reacting an organicpolyisocyanate with a polyester polyol such as those described above canbe used. The organic polyisocyanate can be reacted with a polyol so thatthe OH/NCO equivalent ratio is greater than 1:1 so that the resultantproduct contains free hydroxyl groups. The organic polyisocyanate whichcan be used in preparing the polyurethane polyols can be an aliphatic oraromatic polyisocyanate or a mixture. Diisocyanates can be used,although higher polyisocyanates such as triisocyanates can also be used,but they do result in higher viscosities.

Examples of suitable diisocyanates include 4,4′-diphenylmethanediisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanateand 4,4′-methylenebis(cyclohexyl isocyanate). Examples of suitablehigher functionality polyisocyanates include polymethylene polyphenolisocyanates.

At least a portion, and in certain instances all of the acid functionalgroups can be silylated. Alternatively at least a portion, and incertain instances all of the acid functional groups can be converted tohydroxyl groups by reaction with an epoxide. In certain embodiments theepoxide is a monofunctional epoxide such as ethylene oxide, butyleneoxide, propylene oxide, cyclohexane oxide, glycidyl ethers, and glycidylesters and then silylated. The equivalent ratio of epoxy to acid on theester can range from 0.1:1 to 2:1. In another embodiment, an aliphaticdiol, such a 1,2-propanediol, can be used in place of the epoxide.

In one embodiment, the components that form the composition furthercomprise at least one compound having the following structure (X):

For example, the silylated compound can be the reaction product oftrimethylolpropane, methylhexahydrophthalic anhydride, propylene oxide,and hexamethyl disylizid reacted at a ratio of 1:3:3:3.

Other useful materials having a linkage selected from an ester linkage,a urethane linkage, a urea linkage, an amide linkage, siloxane linkage,and an ether linkage and at least one reactive functional group whichare suitable for silylation are disclosed above in the discussion ofsuitable additional polymers.

Alternatively, useful reactants include acrylic polymers containinghydroxyl groups blocked with hydrolyzable siloxy groups (polymerized forexample from vinyl monomers and trimethyl siloxy methylmethacrylate)such as are disclosed in I. Azuma et al., “Acrylic Oligomer for HighSolid Automotive Top Coating System Having Excellent Acid Resistance”,Progress in Organic Coatings 32 (1997) 1-7, which is incorporated hereinby reference.

In one embodiment, the present invention is directed to compositions aspreviously described wherein the silyl-blocked reactant, when added tothe other components which form the coating composition, is present inthe composition in an amount ranging from 0.1 to 90 weight percent basedon total weight of the resin solids of the components which form thecoating composition. In another embodiment, the present invention isdirected to compositions as previously described wherein thesilyl-blocked reactant, when added to the other components which formthe coating composition, is present in the coating composition in anamount of at least 0.1 weight percent based on total weight of the resinsolids of the components which form the coating composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the silyl-blocked reactant, when added tothe other components which form the coating composition, is present inthe coating composition in an amount of at least 1 weight percent basedon total weight of the resin solids of the components which form thecoating composition. In another embodiment, the present invention isdirected to compositions as previously described wherein thesilyl-blocked reactant, when added to the other components which formthe coating composition in an amount of at least 5 weight percent basedon total weight of the resin solids of the components which form thecoating composition.

In yet another embodiment, the present invention is directed tocompositions as previously described wherein the silyl-blocked reactant,when added to the other components which form the coating composition,is present in the coating composition in an amount less than 60 weightpercent based on total weight of the resin solids of the componentswhich form the coating composition. In a further embodiment, the presentinvention is directed to compositions as previously described whereinthe silyl-blocked reactant, when added to the other components whichform the coating composition, is present in the coating composition inan amount less than 30 weight percent based on total weight of the resinsolids of the components which form the coating composition. In anotherembodiment, the present invention is directed to compositions aspreviously described wherein the silyl-blocked reactant, when added tothe other components which form the coating composition, is present inthe coating composition in an amount less than 10 weight percent basedon total weight of the resin solids of the components which form thecoating composition. The amount of silyl-blocked reactant may rangebetween any combination of these values inclusive of the recited values.

In a further embodiment, the present invention is directed tocompositions as previously described formed from components comprisingat least one film forming material different from the at least onepolysiloxane (a). This film forming material can be a polymer, inaddition to the at least one polysiloxane (a), comprising at least onefunctional group reactive with at least one functional group of the atleast one polysiloxane (a), and the at least one curing agent, ifpresent. In one embodiment, this at least one additional polymer canhave at least one reactive functional group selected from a hydroxylgroup, a carbamate group, an epoxy group, an isocyanate group, and acarboxyl group. In another embodiment, the additional polymer can haveat least one reactive functional group selected from a hydroxyl group,and a carbamate group.

The additional polymer may contain one or more reactive functionalgroups selected from hydroxyl groups, carboxyl groups, isocyanategroups, blocked polyisocyanate groups, primary amine groups, secondaryamine groups, tertiary amine groups, amide groups, carbamate groups,urea groups, urethane groups, vinyl groups, acrylate groups, ananhydride group, a hydroxy alkylamide group, epoxy groups, and mixturesof any of the foregoing.

Nonlimiting examples of suitable hydroxyl group-containing additionalpolymers include acrylic polyols, polyester polyols, polyurethanepolyols, polyether polyols, and mixtures of any of the foregoing. Theadditional polymer can be an acrylic polyol that can have a hydroxylequivalent weight ranging from 1000 to 100 grams per solid equivalent.

Suitable hydroxyl group or carboxyl group-containing acrylic polymerscan be prepared from polymerizable ethylenically unsaturated monomersand can be copolymers of (meth)acrylic acid or hydroxylalkyl esters of(meth)acrylic acid with one or more other polymerizable ethylenicallyunsaturated monomers such as alkyl esters of (meth)acrylic acidincluding methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate and 2-ethyl hexylacrylate, and vinyl aromatic compoundssuch as styrene, alpha-methyl styrene, and vinyl toluene. As usedherein, “(meth)acrylate” and like terms are intended to include bothacrylates and methacrylates.

The acrylic polymer can be prepared from ethylenically unsaturated,beta-hydroxy ester functional monomers. Such monomers can be derivedfrom the reaction of an ethylenically unsaturated acid functionalmonomer, such as monocarboxylic acids, for example, acrylic acid, and anepoxy compound which does not participate in the free radical initiatedpolymerization with the unsaturated acid monomer. Nonlimiting examplesof such epoxy compounds are glycidyl ethers and esters. Nonlimitingexamples of suitable glycidyl ethers comprise glycidyl ethers ofalcohols and phenols such as butyl glycidyl ether, octyl glycidyl ether,phenyl glycidyl ether, and the like. Nonlimiting examples of suitableglycidyl esters include those which are commercially available fromShell Chemical Company under the tradename CARDURA E and from ExxonChemical Company under the tradename GLYDEXX-10. Alternatively, thebeta-hydroxy ester functional monomers are prepared from anethylenically unsaturated, epoxy functional monomer, for exampleglycidyl (meth)acrylate and allyl glycidyl ether, and a saturatedcarboxylic acid, such as a saturated monocarboxylic acid, for exampleisostearic acid.

Epoxy functional groups can be incorporated into the polymer preparedfrom polymerizable ethylenically unsaturated monomers by copolymerizingoxirane group-containing monomers, for example glycidyl (meth)acrylateand allyl glycidyl ether, with other polymerizable ethylenicallyunsaturated monomers, such as those discussed above. Preparation of suchepoxy functional acrylic polymers is described in detail in U.S. Pat.No. 4,001,156 at columns 3 to 6, which columns are specificallyincorporated herein by reference.

Carbamate functional groups can be incorporated into the polymerprepared from polymerizable ethylenically unsaturated monomers bycopolymerizing, for example, the above-described ethylenicallyunsaturated monomers with a carbamate functional vinyl monomer such as acarbamate functional alkyl ester of methacrylic acid. Useful carbamatefunctional alkyl esters can be prepared by reacting, for example, ahydroxyalkyl carbamate (which can be the reaction product of ammonia andethylene carbonate or propylene carbonate) with methacrylic anhydride.

Other useful carbamate functional vinyl monomers include, for instance,the reaction product of hydroxyethyl methacrylate,isophorone-diisocyanate, and hydroxypropyl carbamate; or the reactionproduct of hydroxypropyl methacrylate, isophorone diisocyanate, andmethanol. Still other carbamate functional vinyl monomers may be used,such as the reaction product of isocyanic acid (HNCO) with a hydroxylfunctional acrylic or methacrylic monomer such as hydroxyethyl acrylate,and those monomers described in U.S. Pat. No. 3,479,328, which isincorporated herein by reference.

Carbamate functional groups also can be incorporated into the acrylicpolymer by reacting a hydroxyl functional acrylic polymer with a lowmolecular weight alkyl carbamate such as methyl carbamate. Pendantcarbamate groups also can be incorporated into the acrylic polymer by a“transcarbamoylation” reaction in which a hydroxyl functional acrylicpolymer is reacted with a low molecular weight carbamate derived from analcohol or a glycol ether. The carbamate groups can exchange with thehydroxyl groups to yield the carbamate functional acrylic polymer andthe original alcohol or glycol ether. Also, hydroxyl functional acrylicpolymers can be reacted with isocyanic acid to provide pendent carbamategroups. Likewise, hydroxyl functional acrylic polymers can be reactedwith urea to provide pendent carbamate groups.

The polymers prepared from polymerizable ethylenically unsaturatedmonomers can be prepared by solution polymerization techniques, whichare well-known to those skilled in the art, in the presence of suitablecatalysts such as organic peroxides or azo compounds, for examplebenzoyl peroxide or N,N-azobis(isobutylronitrile). The polymerizationcan be carried out in an organic solution in which the monomers aresoluble by techniques conventional in the art. Alternatively, thesepolymers can be prepared by aqueous emulsion or dispersionpolymerization techniques which are well-known in the art. The ratio ofreactants and reaction conditions are selected to result in an acrylicpolymer with the desired pendent functionality.

Polyester polymers also are useful in the compositions of the inventionas the additional polymer. Useful polyester polymers can comprise thecondensation products of polyhydric alcohols and polycarboxylic acids.Nonlimiting examples of suitable polyhydric alcohols include ethyleneglycol, neopentyl glycol, trimethylol propane, and pentaerythritol.Nonlimiting examples of suitable polycarboxylic acids include adipicacid, 1,4-cyclohexyl dicarboxylic acid, and hexahydrophthalic acid.Besides the polycarboxylic acids mentioned above, functional equivalentsof the acids such as anhydrides where they exist or lower alkyl estersof the acids such as the methyl esters can be used. Also, small amountsof monocarboxylic acids such as stearic acid can be used. The ratio ofreactants and reaction conditions are selected to result in a polyesterpolymer with the desired pendent functionality, i.e., carboxyl orhydroxyl functionality.

For example, hydroxyl group-containing polyesters can be prepared byreacting an anhydride of a dicarboxylic acid such as hexahydrophthalicanhydride with a diol such as neopentyl glycol in a 1:2 molar ratio.Where it is desired to enhance air-drying, suitable drying oil fattyacids may be used and can include those derived from linseed oil, soyabean oil, tall oil, dehydrated castor oil, or tung oil.

Carbamate functional polyesters can be prepared by first forming ahydroxyalkyl carbamate that can be reacted with the polyacids andpolyols used in forming the polyester. Alternatively, terminal carbamatefunctional groups can be incorporated into the polyester by reactingisocyanic acid with a hydroxy functional polyester. Also, carbamatefunctionality can be incorporated into the polyester by reacting ahydroxyl polyester with a urea. Additionally, carbamate groups can beincorporated into the polyester by a transcarbamoylation reaction.Preparation of suitable carbamate functional group-containing polyestersare those described in U.S. Pat. No. 5,593,733 at column 2, line 40 tocolumn 4, line 9, which portion is incorporated herein by reference.

Polyurethane polymers containing terminal isocyanate or hydroxyl groupsalso can be used as the additional polymer in the compositions of theinvention. The polyurethane polyols or NCO-terminated polyurethaneswhich can be used are those prepared by reacting polyols includingpolymeric polyols with polyisocyanates. Polyureas containing terminalisocyanate or primary or secondary amine groups which also can be usedcan be those prepared by reacting polyamines including, but not limitedto, polymeric polyamines with polyisocyanates.

The hydroxyl/isocyanate or amine/isocyanate equivalent ratio can beadjusted and reaction conditions can be selected to obtain the desiredterminal groups. Nonlimiting examples of suitable polyisocyanatesinclude those described in U.S. Pat. No. 4,046,729 at column 5, line 26to column 6, line 28, which portion is incorporated herein by reference.Nonlimiting examples of suitable polyols include those described in U.S.Pat. No. 4,046,729 at column 7, line 52 to column 10, line 35, whichportion is incorporated herein by reference. Nonlimiting examples ofsuitable polyamines include those described in U.S. Pat. No. 4,046,729at column 6, line 61 to column 7, line 32 and in U.S. Pat. No. 3,799,854at column 3, lines 13 to 50, the indicated portions of both areincorporated herein by reference.

Carbamate functional groups can be introduced into the polyurethanepolymers by reacting a polyisocyanate with a polyester having hydroxylfunctionality and containing pendent carbamate groups. Alternatively,the polyurethane can be prepared by reacting a polyisocyanate with apolyester polyol and a hydroxyalkyl carbamate or isocyanic acid asseparate reactants. Nonlimiting examples of suitable polyisocyanatesinclude aromatic isocyanates, (such as 4,4′-diphenylmethanediisocyanate, 1,3-phenylene diisocyanate and toluene diisocyanate) andaliphatic polyisocyanates (such as 1,4-tetramethylene diisocyanate and1,6-hexamethylene diisocyanate). Cycloaliphatic diisocyanates, such as1,4-cyclohexyl diisocyanate and isophorone diisocyanate can be employed.

Nonlimiting examples of suitable polyether polyols include polyalkyleneether polyols such as those having the following structural formulas(VII) or (VIII):

wherein the substituent group R represents hydrogen or a lower alkylgroup of 1 to 5 carbon atoms including mixed substituents, n has a valueranging from 2 to 6, and m has a value ranging from 8 to 100 or higher.Nonlimiting examples of polyalkylene ether polyols includepoly(oxytetramethylene) glycols, poly(oxytetraethylene) glycols,poly(oxy-1,2-propylene) glycols, and poly(oxy-1,2-butylene) glycols.

Also useful can be polyether polyols formed from oxyalkylation ofvarious polyols, for example, but not limited to, glycols such asethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or otherhigher polyols such as trimethylolpropane, pentaerythritol, and thelike. Polyols of higher functionality which can be utilized as indicatedcan be made, for instance, by oxyalkylation of compounds such as sucroseor sorbitol. One oxyalkylation method that can be used is reaction of apolyol with an alkylene oxide, including but not limited to, propyleneor ethylene oxide, in the presence of an acidic or basic catalyst.Specific, nonlimiting examples of polyethers include those sold underthe names TERATHANE and TERACOL, available from E. I. duPont de Nemoursand Co., Inc.

In one embodiment, the present invention is directed to a curedcomposition as previously described in which the at least onefilm-forming material comprises reactive functional groups which arethermally curable functional groups. In an alternative embodiment, atleast one of the reactive functional groups of the film-forming materialcan be curable by ionizing radiation or actinic radiation. In anotheralternative embodiment, the film-forming material can comprise at leastone functional group which is curable by thermal energy and at least onefunctional group which is curable by ionizing or actinic radiation.

Useful radiation-curable groups which can be present as reactivefunctional groups on the polysiloxane include unsaturated groups such asvinyl groups, vinyl ether groups, epoxy groups, maleimide groups,fumarate groups and combinations of the foregoing. In one embodiment,the UV curable groups can include acrylate groups, maleimides,fumarates, and vinyl ethers. Suitable vinyl groups include those havingunsaturated ester groups and vinyl ether groups as discussed below.

In one embodiment, the at least one additional polymer can have a weightaverage molecular weight (Mw) ranging from 1000 to 20,000, as determinedby gel permeation chromatography using a polystyrene standard. Inanother embodiment, the Mw of the at least one additional polymer rangesfrom 1500 to 15,000, and can range from 2000 to 12,000, as determined bygel permeation chromatography using a polystyrene standard.

It should be mentioned that in embodiments where at least one of each ofthe at least one polysiloxane (a) and the at least one additionalpolymer are present during the formation of the composition, thereactive functional groups of the at least one polysiloxane (a) and theadditional polymer can be the same or different, but each must bereactive with at least functional group of the curing agent if employed.Nonlimiting examples of such reactive functional groups include hydroxylgroups, carboxylic acid groups, isocyanate groups, blocked isocyanategroups carboxylate groups, primary amine groups, secondary amine groups,amide groups, carbamate groups, anhydride groups, hydroxy alkylamidegroups, and epoxy groups.

In an embodiment of the present invention, the additional polymer havingat least one reactive functional group, if employed, is generallypresent, when added to the other components in the composition, in anamount of at least 2 percent by weight. That additional polymer can bepresent in an amount of at least 5 percent by weight, and is typicallypresent in an amount of at least 10 percent by weight based on totalweight of the resin solids of the components which form the composition.Also the additional polymer having at least one reactive functionalgroup, if employed, is generally present, when added to the othercomponents in the composition, in an amount of less than 80 percent byweight. It can be present in an amount of less than 60 percent byweight, and is typically present in an amount of less than 50 percent byweight based on total weight of the resin solids of the components whichform the composition. The amount of the additional polymer having atleast one reactive functional groups present in the compositions mayrange between any combination of these values inclusive of the recitedvalues.

The compositions of the present invention can be solvent-basedcompositions, water-based compositions, in solid particulate form, thatis, a powder composition, or in the form of a powder slurry or anaqueous dispersion. The components of the present invention used to formthe compositions of the present invention can be dissolved or dispersedin an organic solvent. Nonlimiting examples of suitable organic solventsinclude alcohols, such as butanol; ketones, such as methyl amyl ketone;aromatic hydrocarbons, such as xylene; and glycol ethers, such as,ethylene glycol monobutyl ether; esters; other solvents; and mixtures ofany of the foregoing.

In solvent based compositions, the organic solvent generally is presentin amounts ranging from 5 to 80 percent by weight based on total weightof the resin solids of the components which form the composition, andcan be present in an amount ranging from 30 to 50 percent by weight,inclusive of the recited values. The compositions as described above canhave a total solids content ranging from 40 to 75 percent by weightbased on total weight of the resin solids of the components which formthe composition, and can have a total solids content ranging from 50 to70 percent by weight, inclusive of the recited values. Alternatively,the inventive compositions can be in solid particulate form suitable foruse as a powder coating, or suitable for dispersion in a liquid mediumsuch as water for use as a powder slurry.

In a further embodiment where the compositions as previously describedare formed from at least one reactant, a catalyst is additionallypresent during the composition's formation. In one embodiment, thecatalyst is present in an amount sufficient to accelerate the reactionbetween at least one reactive functional group of the reactant and atleast one reactive functional group of the at least one polysiloxane(a). In one embodiment, the catalyst is an acid catalyst.

Nonlimiting examples of suitable catalysts include acidic materials, forexample, acid phosphates, such as phenyl acid phosphate, and substitutedor unsubstituted sulfonic acids such as dodecylbenzene sulfonic acid orpara-toluene sulfonic acid. Non-limiting examples of suitable catalystsfor reactions between isocyanate groups and hydroxyl groups include tincatalysts such as dibutyl tin dilaurate. Non-limiting examples of epoxyacid base catalysts include tertiary amines such as N,N′-dimethyldodecylamine catalysts. In another embodiment, the catalyst can be aphosphatized polyester or a phosphatized epoxy. In this embodiment, thecatalyst can be, for example, the reaction product of phosphoric acidand a bisphenol A diglycidyl ether having two hydrogenated phenolicrings, such as DRH-151, which is commercially available from ShellChemical Co. The catalyst can be present, when added to the othercomponents of the composition, in an amount ranging from 0.1 to 5.0percent by weight, and is typically present in an amount ranging from0.5 to 1.5 percent by weight based on the total weight of the resinsolids of the components which form the composition, inclusive of therecited values.

In another embodiment, additional components can be present during theformation of the compositions as previously described. These additionalcomponents include, but are not limited to, flexibilizers, plasticizers,surface active agents as defined herein (such as polysiloxanes),thixotropic agents, anti-gassing agents, organic cosolvents, flowcontrollers, hindered amine light stabilizers, anti-oxidants, UV lightabsorbers, coloring agents or tints, and similar additives conventionalin the art, as well as mixtures of any of the foregoing can be includedin the composition. These additional ingredients can present, when addedto the other components of the composition, in an amount up to 40percent by weight based on the total weight of the resin solids of thecomponents which form the composition.

In yet another embodiment of the present invention, at least one surfaceactive agent can be present during the formation of the compositions aspreviously described. The at least one surface active agent can beselected from anionic, nonionic, and cationic surface active agents.

As used herein, by “surface active agent” is meant any material whichtends to lower the solid surface tension or surface energy of the curedcomposition or coating. That is, the cured composition or coating formedfrom a composition comprising a surface active agent has a lower solidsurface tension or surface energy than a cured coating formed from theanalogous composition which does not contain the surface active agent.

For purposes of the present invention, solid surface tension can bemeasured according to the Owens-Wendt method using a Rame'-Hart ContactAngle Goniometer with distilled water and methylene iodide as reagents.Generally, a 0.02 cc drop of one reagent is placed upon the curedcoating surface and the contact angle and its complement are measuredusing a standard microscope equipped with the goniometer. The contactangle and its complement are measured for each of three drops. Theprocess is then repeated using the other reagent. An average value iscalculated for the six measurements for each of the reagents. The solidsurface tension is then calculated using the Owens-Wendt equation:

{γl(1+cos Φ)}/2=(γl ^(d)γ_(s) ^(d))^(1/2)+(γl ^(p)γ_(s) ^(p))^(1/2)

where γl is the surface tension of the liquid (methylene iodide=50.8,distilled water=72.8) and γ^(d) and γ^(p) are the dispersion and polarcomponents (methylene iodide γ^(d)=49.5, γ^(p)=1.3; distilled waterγ^(d)=21.8, γ^(p)=51.0); the values for Φ measured and the cos Φdetermined. Two equations are then setup, one for methylene iodide andone for water. The only unknowns are γ_(s) ^(d) and γ_(s) ^(p). The twoequations are then solved for the two unknowns. The two componentscombined represent the total solid surface tension.

The at least one surface active agent can be selected from amphiphilic,reactive functional group-containing polysiloxanes, amphiphilicfluoropolymers, and mixtures of any of the foregoing. With reference towater-soluble or water-dispersible amphiphilic materials, the term“amphiphilic” means a polymer having a generally hydrophilic polar endand a water-insoluble generally hydrophobic end. Nonlimiting examples ofsuitable functional group-containing polysiloxanes for use as surfaceactive agents include the at least one polysiloxane (a) described above.Nonlimiting examples of suitable amphiphilic fluoropolymers includefluoroethylene-alkyl vinyl ether alternating copolymers (such as thosedescribed in U.S. Pat. No. 4,345,057) available from Asahi Glass Companyunder the tradename LUMIFLON; fluorosurfactants, such as thefluoroaliphatic polymeric esters commercially available from 3M of St.Paul, Minn. under the tradename FLUORAD; functionalized perfluorinatedmaterials such as 1H,1H-perfluoro-nonanol commercially available fromFluoroChem USA; and perfluorinated (meth)acrylate resins.

Nonlimiting examples of other surface active agents suitable for use inthe cured composition or coating of the present invention can includeanionic, nonionic and cationic surface active agents.

Nonlimiting examples of suitable anionic surface active agents includesulfates or sulfonates. Specific nonlimiting examples include higheralkyl mononuclear aromatic sulfonates such as the higher alkyl benzenesulfonates containing from 10 to 16 carbon atoms in the alkyl group anda straight- or branched-chain, e.g., the sodium salts of decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl benzene sulfonateand the higher alkyl toluene, xylene and phenol sulfonates; alkylnaphthalene sulfonate, and sodium dinonyl naphthalene sulfonate. Othernonlimiting examples of suitable anionic surface active agents includeolefin sulfonates, including long chain alkenylene sulfonates, longchain hydroxyalkane sulfonates, and mixtures of any of the foregoing. Asused herein, “long chain” refers to a chain having greater than 8 carbonatoms. Nonlimiting examples of other sulfate or sulfonate detergents areparaffin sulfonates such as the reaction products of alpha olefins andbisulfites (e.g., sodium bisulfite). Also comprised are sulfates ofhigher alcohols, such as sodium lauryl sulfate, sodium tallow alcoholsulfate, or sulfates of mono-or di-glycerides of fatty acids (e.g.,stearic monoglyceride monosulfate), alkyl poly(ethoxy)ether sulfatesincluding, but not limited to, the sulfates of the condensation productsof ethylene oxide and lauryl alcohol (usually having 1-5 ethenoxy groupsper molecule); lauryl or other higher alkyl glyceryl ether sulfonates;aromatic poly(ethenoxy)ether sulfates including, but not limited to, thesulfates of the condensation products of ethylene oxide and nonyl phenol(usually having 1-20 oxyethylene groups per molecule).

Further nonlimiting examples include salts of sulfated aliphaticalcohol, alkyl ether sulfate or alkyl aryl ethoxy sulfate available fromRhone-Poulenc under the general tradename ABEX. Phosphate mono-ordi-ester type anionic surface active agents also can be used. Theseanionic surface active agents are well known in the art and arecommercially available under the general trademark GAFAC from GAFCorporation and under the general trademark TRITON from Rohm & HaasCompany.

Nonlimiting examples of nonionic surface active agents suitable for usein the cured composition or coating of the present invention includethose containing ether linkages and which are represented by thefollowing general formula: RO(R′O)_(n)H; wherein the substituent group Rrepresents a hydrocarbon group containing 6 to 60 carbon atoms, thesubstituent group R′ represents an alkylene group containing 2 or 3carbon atoms, and mixtures of any of the foregoing, and n is an integerranging from 2 to 100.

Such nonionic surface active agents can be prepared by treating fattyalcohols or alkyl-substituted phenols with an excess of ethylene orpropylene oxide. The alkyl carbon chain may contain from 14 to 40 carbonatoms and may be derived from a long chain fatty alcohol such as oleylalcohol or stearyl alcohol. Nonionic polyoxyethylene surface activeagents of the type represented by the formula above are commerciallyavailable under the general trade designation SURFYNOL from Air ProductsChemicals, Inc.; PLURONIC or TETRONIC from BASF Corporation; TERGITOLfrom Union Carbide; and SURFONIC from Huntsman Corporation. Othernonlimiting examples of suitable nonionic surface active agents includeblock copolymers of ethylene oxide and propylene oxide based on a glycolsuch as ethylene glycol or propylene glycol including, but not limitedto, those available from BASF Corporation under the general tradedesignation PLURONIC.

As indicated above, cationic surface active agents also can be used.Nonlimiting examples of cationic surface active agents suitable for usein the cured compositions or coatings of the present invention includeacid salts of alkyl amines such as ARMAC HT, an acetic acid salt ofn-alkyl amine available from Akzo Nobel Chemicals; imidazolinederivatives such as CALGENE C-100 available from Calgene Chemicals Inc.;ethoxylated amines or amides such as DETHOX Amine C-5, a cocoamineethoxylate available from Deforest Enterprises; ethoxylated fatty aminessuch as ETHOX TAM available from Ethox Chemicals, Inc.; and glycerylesters such as LEXEMUL AR, a glyceryl stearate/stearaidoethyldiethylamine available from Inolex Chemical Co.

Other examples of suitable surface active agents can includepolyacrylates. Nonlimiting examples of suitable polyacrylates includehomopolymers and copolymers of acrylate monomers, for examplepolybutylacrylate and copolymers derived from acrylate monomers (such asethyl (meth)acrylate, 2-ethylhexylacrylate, butyl (meth)acrylate andisobutyl acrylate), and hydroxy ethyl(meth)acrylate and (meth)acrylicacid monomers. In one embodiment, the polyacrylate can have amino andhydroxy functionality. Suitable amino and hydroxyl functional acrylatesare disclosed in Example 26 below and in U.S. Pat. No. 6,013,733, whichis incorporated herein by reference. Another example of a useful aminoand hydroxyl functional copolymer is a copolymer of hydroxy ethylacrylate, 2-ethylhexylacrylate, isobutyl acrylate and dimethylaminoethylmethacrylate. In another embodiment, the polyacrylate can have acidfunctionality, which can be provided, for example, by including acidfunctional monomers such as (meth)acrylic acid in the components used toprepare the polyacrylate. In another embodiment, the polyacrylate canhave acid functionality and hydroxyl functionality, which can beprovided, for example, by including acid functional monomers such as(meth)acrylic acid and hydroxyl functional monomers such as hydroxyethyl (meth)acrylate in the components used to prepare the polyacrylate.

In one embodiment, the present invention is directed to a powdercomposition formed from components comprising:

(a) at least one surface active agent comprising:

(i) at least one polysiloxane comprising at least one reactivefunctional group, the at least one polysiloxane comprising at least oneof the following structural units (I)

R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)

 wherein each R¹, which may be identical or different, represents H, OH,a monovalent hydrocarbon group or a monovalent siloxane group; each R²,which may be identical or different, represents a group comprising atleast one reactive functional group, wherein m and n fulfill therequirements of 0<n<4, 0<m<4 and 2≦(m+n)<4; and

(ii) at least one polyacrylate surface active agent having at least onefunctional group selected from amino and hydroxyl functionality, acidfunctionality and acid and hydroxyl functionality; and

(b) a plurality of particles; wherein each component is different.

In yet another embodiment, the present invention is directed to a coatedsubstrate comprising a substrate and a composition coated over thesubstrate, wherein the composition is selected from any of the foregoingcompositions. In still another embodiment, the present invention isdirected to a method of coating a substrate which comprises applying acomposition over the substrate, wherein the composition is selected fromany of the foregoing compositions. In another embodiment, the presentinvention is directed to a method for forming a cured coating on asubstrate comprising applying over the substrate a coating composition,wherein the composition is selected from any of the foregoingcompositions.

In another embodiment, the present invention is directed to a method ofcoating a substrate further comprising a step of curing the compositionafter application to the substrate. The components used to form thecompositions in these embodiments can be selected from the componentsdiscussed above, and additional components also can be selected fromthose recited above.

As used herein, a composition “over a substrate” refers to a compositiondirectly applied to at least a portion of the substrate, as well as acomposition applied to any coating material which was previously appliedto at least a portion of the substrate.

The compositions of the present invention can be applied over virtuallyany substrate including wood, metals, glass, cloth, plastic, foam,polymeric substrates such as elastomeric substrates, and the like. Inone embodiment, the present invention is directed to a coated substrateas previously described wherein the coated substrate is a flexiblesubstrate. In another embodiment, the present invention is directed to acoated substrate as previously described wherein the coated substrate isa rigid substrate.

In a further embodiment, the present invention is directed to coatedsubstrates as previously described wherein the coated substrate is aceramic substrate. In still another embodiment, the present invention isdirected to coated substrates as previously described wherein the coatedsubstrate is a polymeric substrate. In another embodiment, the presentinvention is directed to a coated metallic substrate comprising ametallic substrate and a composition coated over the metallic substrate,wherein the composition is selected from any of the foregoingcompositions. The components used to form the compositions in theseembodiments can be selected from the components discussed above, andadditional components also can be selected from those recited above.

A further embodiment of the present invention is directed to a coatedautomobile substrate comprising an automobile substrate and acomposition coated over the automobile substrate, wherein thecomposition is selected from any of the foregoing compositions. In yetanother embodiment, the present invention is directed to a method ofmaking a coated automobile substrate comprising providing an automobilesubstrate and applying over the automotive substrate a compositionselected from any of the foregoing compositions. Again, the componentsused to form the compositions in these embodiments can be selected fromthe components discussed above, and additional components also can beselected from those recited above.

Suitable flexible elastomeric substrates can include any of thethermoplastic or thermoset synthetic materials well known in the art.Nonlimiting examples of suitable flexible elastomeric substratematerials include polyethylene, polypropylene, thermoplastic polyolefin(“TPO”), reaction injected molded polyurethane (“RIM”), andthermoplastic polyurethane (“TPU”).

Nonlimiting examples of thermoset materials useful as substrates inconnection with the present invention include polyesters, epoxides,phenolics, polyurethanes such as “RIM” thermoset materials, and mixturesof any of the foregoing. Nonlimiting examples of suitable thermoplasticmaterials include thermoplastic polyolefins such as polyethylene,polypropylene, polyamides such as nylon, thermoplastic polyurethanes,thermoplastic polyesters, acrylic polymers, vinyl polymers,polycarbonates, acrylonitrile-butadiene-styrene (“ABS”) copolymers,ethylene propylene diene terpolymer (“EPDM”) rubber, copolymers, andmixtures of any of the foregoing.

Nonlimiting examples of suitable metal substrates include ferrous metals(e.g., iron, steel, and alloys thereof), nonferrous metals (e.g.,aluminum, zinc, magnesium, and alloys thereof), and mixtures of any ofthe foregoing. In the particular use of automobile components, thesubstrate can be formed from cold rolled steel, electrogalvanized steelsuch as hot dip electrogalvanized steel, electrogalvanized iron-zincsteel, aluminum, and magnesium.

When the substrates are used as components to fabricate automotivevehicles (including, but not limited to, automobiles, trucks andtractors) they can have any shape, and can be selected from the metallicand flexible substrates described above. Typical shapes of automotivebody components can include bodies (frames), hoods, doors, mirrorhousings, fenders, bumpers, and trim for automotive vehicles.

In a further embodiment, the present invention is directed to coatedautomotive substrates as previously described wherein the coatedautomotive substrate is a hood. In another embodiment, the presentinvention is directed to coated automotive substrates as previouslydescribed wherein the coated automotive substrate is a door. In anotherembodiment, the present invention is directed to coated automotivesubstrates as previously described wherein the coated automotivesubstrate is a fender. In another embodiment, the present invention isdirected to coated automotive substrates as previously described whereinthe coated automotive substrate is a housing for a mirror. In anotherembodiment, the present invention is directed to coated automotivesubstrates as previously described wherein the coated automotivesubstrate is a quarterpanel. The components used to form thecompositions used to coat the automotive substrates in these embodimentscan be selected from the components discussed above.

In embodiments of the present invention directed to automotiveapplications, the cured compositions can be, for example, theelectrodeposition coating, the primer coating, the basecoat, and/or thetopcoat. Suitable topcoats include monocoats and basecoat/clearcoatcomposites. Monocoats are formed from one or more layers of a coloredcoating composition. Basecoat/clearcoat composites comprise one or morelayers of a colored basecoat composition, and one or more layers of aclearcoating composition, wherein the basecoat composition has at leastone component which is different from the clearcoat composition. In theembodiments of the present invention directed to automotiveapplications, the clearcoat can be transparent after application.

In one embodiment, the particles can be dispersed or suspended in acarrier and applied to the polymeric substrate or polymeric coating,i.e., the electrodeposited coating, the primer coating, or the topcoatdiscussed above. The carrier can be water, a solvent, a surfactant andthe like, as well as mixtures thereof.

In another embodiment, the present invention is directed tomulti-component composite coating compositions comprising a basecoatdeposited from a pigmented coating composition, and a topcoatingcomposition applied over the basecoat, wherein the topcoatingcomposition is selected from any of the compositions previouslydescribed.

In one embodiment, the present invention is directed to amulti-component composite coating composition as previously described,wherein the topcoating composition is transparent after curing and isselected from any of the compositions previously described. Thecomponents used to form the topcoating composition in these embodimentscan be selected from the coating components discussed above.

The basecoat and transparent topcoat (i.e., clearcoat) compositions usedin the multi-component composite coating compositions of the presentinvention in certain instances can be formulated into liquid high solidscoating compositions, that is, compositions generally containing 40percent, or in certain instances greater than 50 percent by weight resinsolids. The solids content can be determined by heating a sample of thecomposition to 105° C. to 110° C. for 1-2 hours to drive off thevolatile material, and subsequently measuring relative weight loss. Asaforementioned, although the compositions can be liquid coatingcompositions, they also can be formulated as powder coatingcompositions.

The coating composition of the basecoat in the color-plus-clear systemcan be any of the compositions useful in coatings applications,particularly automotive applications. The coating composition of thebasecoat can comprise a resinous binder and a pigment to act as thecolorant. Nonlimiting examples of resinous binders are acrylic polymers,polyesters, alkyds, and polyurethanes.

The resinous binders for the basecoat can be organic solvent-basedmaterials such as those described in U.S. Pat. No. 4,220,679, notecolumn 2, line 24 continuing through column 4, line 40, which portionsis incorporated by reference. Also, water-based coating compositionssuch as those described in U.S. Pat. Nos. 4,403,003, 4,147,679 and5,071,904 can be used as the binder in the basecoat composition. TheseU.S. patents are incorporated herein by reference.

The basecoat composition can comprise one or more pigments as colorants.Nonlimiting examples of suitable metallic pigments include aluminumflake, copper bronze flake, and metal oxide coated mica.

Besides the metallic pigments, the basecoat compositions can containnonmetallic color pigments conventionally used in surface coatings suchas inorganic pigments such as titanium dioxide, iron oxide, chromiumoxide, lead chromate, and carbon black; and organic pigments such asphthalocyanine blue and phthalocyanine green.

Optional ingredients in the basecoat composition can comprise thosewhich are well known in the art of formulating surface coatings and cancomprise surface active agents, flow control agents, thixotropic agents,fillers, anti-gassing agents, organic co-solvents, catalysts, and othercustomary auxiliaries. Nonlimiting examples of these materials andsuitable amounts are described in U.S. Pat. Nos. 4,220,679; 4,403,003;4,147,769; and 5,071,904, which patents are incorporated herein byreference.

The basecoat compositions can be applied to the substrate by anyconventional coating technique such as brushing, spraying, dipping, orflowing. Spray techniques and equipment for air spraying, airless spray,and electrostatic spraying in either manual or automatic methods, knownin the art can be used.

During application of the basecoat to the substrate, the film thicknessof the basecoat formed on the substrate can range from 0.1 to 5 mils. Inanother embodiment, the film thickness of the basecoat formed on thesubstrate can range 0.1 to 1 mils, and can be 0.4 mils.

After forming a film of the basecoat on the substrate, the basecoat canbe cured or alternatively given a drying step in which solvent is drivenout of the basecoat film by heating or an air drying period beforeapplication of the clearcoat. Suitable drying conditions may depend onthe particular basecoat composition, and on the ambient humidity if thecomposition is water-borne, but a drying time from 1 to 15 minutes at atemperature of 750 to 200° F. (210 to 93° C.) can be adequate.

The transparent or clear topcoat composition can be applied to thebasecoat by any conventional coating technique, including, but notlimited to, compressed air spraying, electrostatic spraying, and eithermanual or automatic methods. The transparent topcoat can be applied to acured or to a dried basecoat before the basecoat has been cured. In thelatter instance, the two coatings can then be heated to cure bothcoating layers simultaneously. Typical curing conditions can range from50° F. to 475° F. (10° C. to 246° C.) for 1 to 30 minutes.Alternatively, the transparent topcoat can be cured by ionizing oractinic radiation or the combination of thermal energy and ionizing oractinic radiation as described in detail above. The clearcoatingthickness (dry film thickness) can be 1 to 6 mils.

A second topcoat coating composition can be applied to the first topcoatto form a “clear-on-clear” topcoat. The first topcoat coatingcomposition can be applied over at least a portion of the basecoat asdescribed above. The second topcoat coating composition can be appliedto a cured or to a dried first topcoat before the basecoat and firsttopcoat have been cured. The basecoat, the first topcoat, and the secondtopcoat then can be heated to cure the three coatings simultaneously.

It should be understood that the second transparent topcoat and thefirst transparent topcoat coating compositions can be the same ordifferent provided that, when applied wet-on-wet, one topcoat does notsubstantially interfere with the curing of the other, for example byinhibiting solvent/water evaporation from a lower layer. Moreover, thefirst topcoat, the second topcoat or both can be the coating compositionof the present invention. The first transparent topcoat coatingcomposition can be virtually any transparent topcoating compositionknown to those skilled in the art. The first transparent topcoatcomposition can be water-borne or solventborne, or, alternatively, insolid particulate form, i.e., a powder coating.

Nonlimiting examples of suitable first topcoating compositions includecrosslinkable coating compositions comprising at least onethermosettable coating material and at least one curing agent. Suitablewaterborne clearcoats are disclosed in U.S. Pat. No. 5,098,947, whichpatent is incorporated herein by reference, and are based onwater-soluble acrylic resins. Useful solvent borne clearcoats aredisclosed in U.S. Pat. Nos. 5,196,485 and 5,814,410, which patents areincorporated herein by reference, and include polyepoxides and polyacidcuring agents. Suitable powder clearcoats are described in U.S. Pat. No.5,663,240, which patent is incorporated herein by reference, and includeepoxy functional acrylic copolymers and polycarboxylic acid curingagents.

Typically, after forming the first topcoat over at least a portion ofthe basecoat, the first topcoat is given a drying step in which solventis driven out of the film by heating or, alternatively, an air dryingperiod or curing step, before the application of the second topcoat.Suitable drying conditions will depend on the particular first topcoatcomposition, and on the ambient humidity if the composition iswater-borne, but, in general, a drying time from 1 to 15 minutes at atemperature of 750 to 200° F. will be adequate.

The polysiloxane-containing second topcoat coating composition of thepresent invention can be applied as described above for the firsttopcoat by any conventional coating application technique. Curingconditions can be those described above for the topcoat. The secondtopcoating dry film thickness can range from 0.1 to 3 mils, andtypically ranges from 0.5 to 2 mils.

It should be mentioned that the polysiloxane-containing coatingcompositions can be advantageously formulated as a “monocoat,” that is,a coating which forms essentially one coating layer when applied to asubstrate. The monocoat coating composition can be pigmented.Nonlimiting examples of suitable pigments include those mentioned above.When employed as a monocoat, the polysiloxane-containing coatingcompositions of the present invention can be applied (by any of theconventional application techniques discussed above) in two or moresuccessive coats, and, in certain instances can be applied with only anambient flash period between coats. The multi-coats when cured can formessentially one coating layer.

In another embodiment, the present invention is directed to a method formaking a multi-component composite comprising (a) applying a pigmentedcomposition to a substrate to form a basecoat; and (b) applying atopcoating composition over at least a portion of the basecoat to form atopcoat thereon, wherein the topcoating composition is selected from anyof the compositions described above. The components used to form thetopcoating composition in this embodiment can be selected from thecoating components discussed above, and additional components also canbe selected from those recited above.

The coatings formed from the compositions according to the presentinvention can have outstanding appearance properties and initial scratch(mar) resistance properties, as well as retained scratch (mar)resistance, which can be evaluated by measuring the gloss of coatedsubstrates before and after abrading of the coated substrates.

In one embodiment, the present invention is directed to methods ofimproving the scratch resistance of a substrate comprising applying tothe substrate any of the inventive compositions described for thesubstrate. In another embodiment, the present invention is directed to amethod of improving the dirt repellency of a substrate comprisingapplying to the comprising any of the inventive compositions describedfor the substrate.

In another embodiment, the present invention is directed to a method forretaining the gloss of a substrate over time comprising applying to thesubstrate comprising any of the inventive compositions described for thesubstrate. In another embodiment, the present invention is directed to amethod for revitalizing the gloss of a substrate comprising applying tothe substrate any of the inventive compositions described for thesubstrate.

The initial 20° gloss of a coated substrate according to the presentinvention can be measured with a 20° NOVO-GLOSS 20 statisticalglossmeter, available from Gardner Instrument Company, Inc. The coatedsubstrate can be subjected to scratch testing by linearly scratching thecoating or substrate with a weighted abrasive paper for ten double rubsusing an Atlas AATCC Scratch Tester, Model CM-5, available from AtlasElectrical Devices Company of Chicago, Ill. The abrasive paper is 3M281Q WETORDRY™ PRODUCTION™ 9 micron polishing paper sheets, which arecommercially available from 3M Company of St. Paul, Minn. Panels arethen rinsed with tap water and carefully patted dry with a paper towel.The 20° gloss is measured on the scratched area of each test panel. Thenumber reported is the percent of the initial gloss retained afterscratch testing, i.e., 100%×scratched gloss/initial gloss. This testmethod is fully disclosed in the examples that follow.

In one embodiment, the present invention is directed to curedcompositions having an initial scratch resistance value such that afterscratch testing greater than 40 percent of initial 20° gloss isretained.

In another embodiment, the present invention is directed to curedcompositions having an initial scratch resistance value such that afterscratch testing greater than 50 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having a retained scratch resistance value such thatafter scratch testing greater than 30 percent of initial 20° gloss isretained. In another embodiment, the present invention is directed tocured compositions having a retained scratch resistance value such thatafter scratch testing greater than 40 percent of initial 20° gloss isretained.

In another embodiment, the present invention is directed to a curedcoating formed from any of the compositions previously described. Inanother embodiment, the cured composition is thermally cured. In anotherembodiment, the cured composition is cured by exposure to ionizingradiation, while in yet another embodiment, the cured composition iscured by exposure to actinic radiation. In another embodiment the curedcomposition is cured by exposure to (1) ionizing radiation or actinicradiation and (2) thermal energy.

In another embodiment, the compositions of the present invention alsocan be useful as decorative or protective coatings for pigmented plastic(elastomeric) substrates, such as those described above, ormold-in-color (“MIC”) plastic substrates. In these applications, thecompositions can be applied directly to the plastic substrate orincluded in the molding matrix. Optionally, an adhesion promoter canfirst be applied directly to the plastic or elastomeric substrate andthe composition applied as a topcoat thereover. The compositions of thepresent invention also can be advantageously formulated as pigmentedcoating compositions for use as primer coatings, as basecoats inmulti-component composite coatings, and as monocoat topcoats includingpigments or colorants. The components used to form the compositions inthese embodiments can be selected from the coating components discussedabove, and additional components also can be selected from those recitedabove.

In another embodiment of the present invention, a transparentthermally-cured composition is provided which comprises a plurality ofparticles within the cured composition. As discussed in greater detailbelow, in such embodiments a first portion of the particles is presentin a surface region of the cured composition in a concentration which ishigher than a concentration of a second portion of particles which ispresent in a bulk region of the cured composition. In certain instances,the BYK Haze value of the cured composition is less than 50, can be lessthan 35, and is often less than 20 as measured using a BYK Haze Glossmeter available from BYK Chemie USA.

As used herein “surface region” of the cured composition means theregion which is generally parallel to the exposed air-surface of thecoated substrate and which has thickness generally extendingperpendicularly from the surface of the cured coating to a depth rangingfrom at least 20 nanometers to 150 nanometers beneath the exposedsurface. In certain embodiments, this thickness of the surface regionranges from at least 20 nanometers to 100 nanometers, and can range fromat least 20 nanometers to 50 nanometers. As used herein, “bulk region”of the cured composition means the region which extends beneath thesurface region and which is generally parallel to the surface of thecoated substrate. The bulk region has a thickness extending from itsinterface with the surface region through the cured coating to thesubstrate or coating layer beneath the cured composition.

In embodiments of the present invention in which the particles have anaverage particle size greater than 50 nanometers, the thickness of thesurface region generally extends perpendicularly from the surface of thecured coating to a depth equal to three times the average particle sizeof the particles, and this surface can extend to a depth equal to twotimes the average particle size of the particles.

The concentration of particles in the cured coating can be characterizedin a variety of ways. For example, the average number density ofparticles (i.e., the average number or population of particles per unitvolume) within the surface region is greater than the average numberdensity within the bulk region. Alternatively, the average volumefraction (i.e., volume occupied by particles/total volume) or averageweight percent per unit volume, i.e., ((the weight of particles within aunit volume of cured coating)/(total weight of the unit volume of curedcoating))×100% of the particles dispersed in the surface region isgreater than the average volume fraction or average weight percent ofparticles within the bulk region.

The concentration of particles (as characterized above) present in thesurface region of the cured coating can be determined, if desired, by avariety of surface analysis techniques well known in the art, such asTransmission Electron Microscopy (“TEM”), Surface Scanning ElectronMicroscopy (“X-SEM”), Atomic Force Microscopy (“AFM”), and X-rayPhotoelectron Spectroscopy.

For example, the concentration of particles present in the surfaceregion of the cured coating may be determined by cross-sectionaltransmission electron microscopy techniques. A useful transmissionelectron microscopy method can be described generally as follows. Acoating composition is applied to a substrate and cured under conditionsappropriate to the composition and substrate. Samples of the curedcoating are then removed or delaminated from the substrate and embeddedin a cured epoxy resin using techniques as are well known in the art.The embedded samples can then be microtomed at room temperature usingtechniques well known in the art, such as by forming a block face. Thesections can be cut using a 45° diamond knife edge mounted in a holderwith a “boat cavity” to hold water. During the cutting process, sectionsfloat to the surface of the water in the boat cavity. Once a few cutsreach an interference color of bright to dark gold (i.e., approximately100 to 150 nanometers thickness), individual samples typically arecollected onto a formvar-carbon coated grid and dried at ambienttemperature on a glass slide. The samples are then placed in a suitabletransmission electron microscope, such as a Philips CM12 TEM, andexamined at various magnifications, such as at 105,000× magnification,for documentation of particle concentration at the surface region, viaelectron micrography. The concentration of particles in a surface regionof a cured coating can be ascertained upon visual inspection of theelectron micrograph, and FIG. 4 provides an example of such an electronmicrograph.

It should be understood that the particles can be present in the surfaceregion such that a portion of the particles at least partially protrudesabove the cured coating surface, essentially unprotected by an organiccoating layer. Alternatively, the particles can be present in thesurface region such that this organic coating layer lies between theparticles and the exposed air-surface interface of the surface region.

In certain embodiments, the cured composition or coating of the presentinvention has an initial 20° gloss (as measured using a 20° NOVO-GLOSS20 statistical glossmeter, available from Gardner Instrument Company) ofgreater than 70, can be greater than 75, and is often greater than 80.This high gloss composition can be curable under ambient or thermalconditions and can be curable by radiation. In one embodiment, the highgloss composition can be cured by ambient or thermal conditions.

Moreover, the cured topcoat can exhibit excellent initial scratch (mar)resistance as well as retained scratch (mar) resistance properties. Thecured topcoat can have an initial scratch (mar) resistance value (asmeasured by first determining the initial 20° gloss as described above,linearly abrading the cured coating surface with a weighted abrasivepaper for ten double rubs using an Atlas AATCC Scratch Tester, ModelCM-5, available from Atlas Electrical Devices Company, and measuring the20° gloss as described above for the abraded surface) such that aftermar testing greater than 40 percent of initial 20° gloss is retained, incertain instances greater than 50 percent of initial 20° gloss isretained, and in other instances greater than 70 percent of initial 20°gloss is retained after abrading the coating surface (that is,100%×scratched gloss/initial gloss).

Also, the cured topcoat of the present invention can have a retainedscratch (mar) resistance (as measured using the scratch test methoddescribed above after the unscratched test panels were subjected tosimulated weathering by QUV exposure to UVA-340 bulbs in a weatheringcabinet available from Q Panel Company) such that greater than 30percent of initial 20° gloss is retained is retained after weathering.In another embodiment, greater than 40 percent of initial 20° gloss isretained, an often greater than 60 percent of initial 20° gloss isretained after weathering.

The cured compositions of the present invention advantageously can beemployed as the transparent topcoat in a cured multi-component compositecoating comprising a basecoat deposited from a pigmented coatingcomposition and the topcoat deposited from a topcoat coatingcomposition. When so employed, the cured topcoat can be deposited fromany topcoating composition described above which comprises particles, incertain instances having a particle size ranging from 1 to 1000nanometers prior to incorporation into the coating composition. Ofcourse whether the haze is too great will depend upon the size,composition and shape of the particles.

In yet another embodiment of the present invention, a composition isprovided which comprises particles dispersed in a composition comprisingone or more thermoplastic materials. As previously described, theconcentration of particles is greater in the surface region than in thebulk region. The composition can be derived from a thermoplasticresinous composition. Nonlimiting examples of suitable thermoplasticmaterials include high molecular weight (i.e., Mw greater than 20,000,greater than 40,000, or greater than 60,000), acrylic polymers,polyolefin polymers, polyamide polymers, and polyester polymers suitablefor use in lacquer dry systems. One nonlimiting example of a class ofthermoplastic materials from which the composition can be derived isfluoropolymer-acrylic copolymers such as those prepared frompolyvinylidene fluoride, for example, KYNAR 500 (available from AusimontUSA, Inc.) and thermoplastic acrylic copolymers, such as ACRYLOID B44(65% methyl methacrylate and 35% ethyl acrylate), available from DockResin, Inc.

In another embodiment, the present invention is directed to a method forretaining the gloss of a polymeric substrate or polymer coated substrateafter a predetermined period of time comprising applying to thesubstrate comprising any of the inventive compositions described for thesubstrate. This predetermined period of time can generally be at least 6months and can be at least one year. In another embodiment, the presentinvention is directed to a method for revitalizing the gloss of apolymeric substrate or polymer coated substrate comprising applying tothe substrate any of the inventive compositions described above.

Illustrating the invention are the following examples which, however,are not to be considered as limiting the invention to their details.Unless otherwise indicated, all parts and percentages in the followingexamples, as well as throughout the specification, are by weight.

EXAMPLES

Example A describes the preparation of a polysiloxane polyol which isthe hydrosilylation reaction product of a pentasiloxane containingsilicon hydride and trimethylolpropane monoallyl ether. Example Bdescribes the preparation of a carbamate functional group-containingpolysiloxane using the polysiloxane of Example A as a starting material.Example C describes the preparation of a carbamate functionalgroup-containing polysiloxane using a commercially available hydroxylfunctional polysiloxane.

Examples AA, BB, CC, DD and EE describe the preparation of varioussilica dispersions which are subsequently incorporated into coatingcompositions.

Examples 1 through 10 describe the preparation of one-pack coatingcompositions which contain aminoplast curing agents.

Comparative Examples 1 through 3 describe the preparation of high solidscoating compositions which were used to form the transparent topcoats incomparative multi-component composite coating compositions. Thecomposition of Example 1 contains no polysiloxane and no inorganicparticles, and the compositions of Examples 2 and 3 contain nopolysiloxane but include inorganic particles in the form of a colloidalsilica dispersion.

Examples 4 and 5 describe the preparation of coating compositions of theinvention which contain a carbamate functional group-containingpolysiloxane and inorganic particles in the form of a colloidal silicadispersion. Example 6 describes the preparation of a coating compositionof the invention which contains a carbamate functional group-containingpolysiloxane and inorganic particles in the form of colloidal silicadispersed in the polysiloxane. Example 7 describes the preparation ofthe coating composition which is the nonsilica containing analogue ofExample 6. Example 8 describes the preparation of a coating compositionwhich contains a carbamate functional group-containing siloxanedifferent from that used in the examples above. Examples 9 and 10describes the preparation of a film forming compositions of theinvention which contains inorganic particles in the form of a fumedsilica dispersion prepared by grinding the fumed silica in the presenceof a polysiloxane prior to incorporation into the composition.

Examples 11 through 17 describe the preparation of coating compositionswhich are prepared as two-component systems, i.e., the compositionscomprise a polyisocyanate curing agent which is added to thecompositions just prior to application.

Comparative Example 11 describes the preparation of a coatingcomposition used to form the transparent topcoat in a multi-componentcomposite coating composition which contains an acrylic polyol and apolyisocyanate curing agent. Comparative Example 12 describes thepreparation of the acid catalyst containing analogue of Example 11.Comparative Example 13 describes the preparation of the aminoplastcontaining analog of Example 11 and Comparative Example 14 describes thepreparation of the acid catalyst containing analogue of Example 13.Example 15 describes the preparation of a coating composition of theinvention which contains the acrylic polyol, both aminoplast andpolyisocyanate curing agents and a polysiloxane polyol. Example 16 isthe acid catalyst containing analogue of Example 15. Example 17describes the preparation of a coating composition of the inventionwhich contains an acrylic polyol, both aminoplast and polyisocyanatecuring agents, acid catalyst, the polysiloxane polyol and inorganicparticles in the form of a colloidal silica dispersed in thepolysiloxane polyol. Example 18 is the analogue of Example 17, butcontaining a higher level of the colloidal silica.

Examples 19 and 20 describe the preparation of respective one-componentand two-component coating compositions of the present invention whichare suitable for application to flexible elastomeric substrates.

Example 21 describes the preparation of epoxy/acid coating compositions.Examples 21A and 21B describe the preparation of comparativecompositions which contain no inorganic particles and Examples 21C-21Ddescribe the preparation of coating compositions of the invention whichcontain varying amounts of the inorganic particles.

Examples 22A to 22I describe the preparation of two-component coatingcompositions which illustrate the effects of lower levels of variouspolysiloxanes in conjunction with inorganic particles in the form ofcolloidal silica.

Example 23 describes the preparation of transparent topcoat coatingcompositions of the present invention (Examples 23A-23C) which wereapplied to respective substrates and subsequently evaluated usingtransmission electron microscopy.

Example 24 describes the preparation of coating compositions of thepresent invention which contain various polysiloxanes in conjunctionwith inorganic particles in the form of colloidal silica. The coatingcomposition was applied to a basecoated substrate and evaluated versus asimilarly applied commercial two-component isocyanate clearcoat(comparative example) for penetration (scratch depth) as a function ofload and scratch distance to determine the critical load at whichcoating failure occurs.

Example 25 describes the preparation of coating compositions of thepresent invention which contain various levels of the polysiloxanepolyol of Example A (Examples 25B to 25G) in conjunction with variouslevels of inorganic particles in the form of colloidal silica.Comparative Example 24A contains polysiloxane polyol but no colloidalsilica.

Example 26 describes the preparation of coating compositions of thepresent invention in solid particulate form (i.e., powder coatingcompositions, Examples 26C and 26D) which contain surface active agentsin conjunction with inorganic particles in the form of aluminum oxide.Comparative Examples 26A and 26B describes powder compositions whichcontain surface active agents but no aluminum oxide.

Example 27 describes the preparation of transparent topcoat coatingcompositions of the present invention.

Example 28 describes the preparation of coating compositions of thepresent invention which contains silylated compounds.

Example 29 describes the preparation of a coating composition of thepresent invention which is cured via a dual cure system.

Example 30 describes the preparation of a coating compositions of thepresent invention.

Example 31 describes the preparation of coating compositions of thepresent invention.

Polysiloxanes Example A

This example describes the preparation of polysiloxane polyol, a productof the hydrosilylation of pentasiloxane with an approximate degree ofpolymerization of 3 to 4, i.e., (Si—O)₃ to (Si—O)₄. The polysiloxanepolyol was prepared from a proportionately scaled-up batch of thefollowing mixture of ingredients in the ratios indicated:

Equivalent Parts By Weight Ingredients Weight Equivalents (kilograms)Charge I: Trimethylolpropane 174.0 756.0 131.54 monoallyl ether ChargeII: MASILWAX BASE¹ 156.7² 594.8 93.21 Charge III: Chloroplatinic acid 10ppm Toluene 0.23 Isopropanol .07 ¹Polysiloxane-containing siliconhydride, commercially available from BASF Corporation. ²Equivalentweight based on mercuric bichloride determination.

To a suitable reaction vessel equipped with a means for maintaining anitrogen blanket, Charge I and an amount of sodium bicarbonateequivalent to 20 to 25 ppm of total monomer solids was added at ambientconditions and the temperature was gradually increased to 75° C. under anitrogen blanket. At that temperature, 5.0% of Charge II was added underagitation, followed by the addition of Charge III, equivalent to 10 ppmof active platinum based on total monomer solids. The reaction was thenallowed to exotherm to 95° C. at which time the remainder of Charge IIwas added at a rate such that the temperature did not exceed 95° C.After completion of this addition, the reaction temperature wasmaintained at 95° C. and monitored by infrared spectroscopy fordisappearance of the silicon hydride absorption band (Si—H, 2150 cm⁻¹).

Example B

This Example describes the preparation of a carbamate-functionalpolysiloxane using the polysiloxane polyol of Example A.

A suitable reaction vessel equipped for vacuum distillation was flushedwith N₂. To the reaction flask was added 1782.9 g of polysiloxane polyolof Example A, 5.48-g of butyl stannoic acid and 16.41 g triphenylphosphite. The reaction was placed under vacuum and heated to atemperature of 140° C. To the resulting mixture was added over a periodof 3 hours, 665.4 g of a 38% solution of 1-methoxy-2-propyl carbamate in1-methoxy-2-propanol. After the addition was completed the temperaturewas increased to 150° C. and held until distillation was complete. Thereaction was cooled to a temperature of 90° C. and brought toatmospheric pressure. The resulting resin was diluted with 825.3 g of1-methoxy-2-propanol.

Example C

This Example describes the preparation of a carbamate-functionalpolysiloxane. A suitable reaction vessel equipped with stirrer,temperature probe, distillation condenser and receiver was flushed withN₂. To the reaction vessel was added 291.9 grams of KR-2001, apolysiloxane available from Shin-Etsu Chemicals, 1.91 grams of butylstannoic acid and 250.4 grams of xylene. The reaction mixture was heatedto a temperature of 140° C. at which time 148.6 grams of methylcarbamate was added over a period of 1 hour. The reaction was held atthat temperature for a period of 3.5 hours.

Silica Dispersions Example AA

This Example describes the preparation of a colloidal silica dispersion.The dispersion was prepared as follows:

To a suitable reaction vessel equipped for vacuum distillation andflushed with N₂ was added 811.9 g of an 88% acrylic polyol solution (40%hydroxy propyl acrylate, 60% butyl methacrylate) in1-methoxy-2-propanol; 544.3 g of colloidal silica (available asORGANOSILICASOL MT-ST from Nissan Chemical Co.); 1.58 g of butylstannoic acid and 3.18 g triphenyl phosphite. The reaction was placedunder vacuum and heated to 140° C. To the resulting mixture was added,over a period of 3 hours, 665.4 g of a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol. After the additionwas complete, the temperature was increased to 150° C. and held at thattemperature until distillation had stopped. The reaction was cooled to90° C. and brought to atmospheric pressure. The resulting resin had ahydroxyl value of 80.51 and was diluted with 251.4 g of1-methoxy-2-propanol.

Example BB

This Example describes a colloidal silica dispersion prepared asdescribed in Example 5 of U.S. Pat. No. 5,853,809 as follows: To asuitable reaction vessel equipped with stirrer and temperature probe andflushed with N₂ was added 858.7 g of the carbamate functional acrylicresin as describe below. The resin was heated to a temperature of 40° C.To the resulting solution was added over a period of 20 minutes, 124.4 gof gamma-isocyanatopropyl triethoxysilane (available as A1310 from OSiSpecialties, a subsidiary of Witco Corporation) diluted in 148.2 g ofamyl acetate and 10.5 g butanol. That temperature was maintained for 3.5hours and the reaction was monitored for completion by infraredspectroscopy. With stirring, 60 g of the resulting resin was added to1500 g of NALCO 1057 (available from Nalco Chemical Co.). The resultingmixture was heated to a temperature of 60° C. and held for a period of19 hours.

The carbamate functional acrylic resin prepared as follows: A suitablereaction flask equipped for vacuum distillation was flushed with N₂ and1670.2 g of 88% acrylic polyol solution, (40% HPA, 60% BMA), in1-methoxy-2-propanol, 4.9 g of butyl stannoic acid and 4.9 g oftriphenyl phosphite added. The reaction was placed under vacuum andheated to a temperature of 140° C. To the resulting mixture was added,over a period of 3 hours, 1263.64 g of a 38% solution of1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol. The resultingdistillate was collected. After the addition was complete, thetemperature was increased to 150° C. and held at that temperature untildistillation had stopped. The reaction was cooled to 90° C. and broughtto atmospheric pressure. The resulting resin had a hydroxyl value of34.48 and was diluted with a mixture of 251.4 g of 1-methoxy-2-propanoland 3-ethoxy ethyl propionate.

Example CC

This Example describes a colloidal silica dispersion prepared asfollows: A suitable reaction vessel equipped for vacuum distillation wasflushed with N₂ To the reaction flask was added 509.6 g of thepolysiloxane polyol of Example A, 566.3 g of ORGANOSILICASOL MA-ST-Mcolloidal silica (available from Nissan Chemicals), 1.57 g of butylstannoic acid and 4.69 g of triphenyl phosphite. The reaction was placedunder vacuum and heated to 140° C. To the resulting mixture was addedover a period of 3 hours 997.9 g of a 38% solution of 1-methoxy-2-propylcarbamate in 1-methoxy-2-propanol. The resulting distillate wascollected. After the feed was complete, the temperature was increased to150° C. and held until distillation was complete. The reaction wascooled to 90° C. and brought to atmospheric pressure. The resultingdispersion was diluted with 160.8 g of 1-methoxy-2-propanol.

Example DD

This Example describes a colloidal silica dispersion prepared asfollows: A suitable reaction vessel equipped for vacuum distillation wasflushed with N₂. To the reaction flask was added 150.7 g of thepolysiloxane polyol of Example A and 500.4 g of ORGANOSILICASOL MT-ST,colloidal silica (available from Nissan Chemicals). The resultingmixture was vacuum distilled at 25° C. for a period of 2 hours and thendiluted with 160.8 g of methyl amyl ketone.

Example EE

This Example describes a fumed silica dispersion prepared as follows: Asuitable mixing container was equipped with a Cowles dispersingagitator. To the container was added 315.3 g of the polysiloxane polyolof Example A, 451.0 g of methyl amyl ketone and 135.2 g of R812 fumedsilica (available from Degussa Corporation). The mixture was agitateduntil all of the R812 silica was dispersed. The dispersion was thenadded to an EIGER Mill for a period of 60 minutes to achieve a grindfineness of 8+ Hegman.

Coating Compositions

The following Examples 1-10 describe the preparation of coatingcompositions of the invention, as well as comparative coatingcompositions, used to form the transparent topcoat in multi-componentcomposite coating compositions. Amounts indicated represent parts byweight. The coating compositions were prepared from a mixture of thefollowing ingredients.

Example Example Example Example Example Example Example Example ExampleExample INGREDIENT 1* 2* 3* 4 5 6 7 8 9 10 Methyl amyl ketone 35.0 35.035.0 35.0 35.0 35.0 35.0 35.0 35.0 40.0 TINUVIN 928¹ 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 3.0 TINUVIN 123² 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.500.50 1.00 RESIMENE 757³ 41.24 41.24 41.24 41.24 41.24 41.24 41.24 41.2441.24 41.24 Flow additive⁴ 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.500.50 Catalyst⁵ 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 — Catalyst⁶— — — — — — — — — 2.50 Carbamate- 93.75 70.17 93.34 69.91 46.73 70.3170.31 70.31 65.63 70.31 functional acrylic resin⁷ Silica dispersion of —23.87 — — 23.87 — — — — — Example AA Silica dispersion of — — 10.4010.40 — — — — — — Example BB Silica dispersion at — — — — — 15.09 — — —— Example CC Silica dispersion of — — — — — — — — 9.23 — Example DDSilica dispersion of — — — — — — — — — 33.33 Example EE Carbamate- — — —18.75 18.75 4.53 18.75 — 18.75 4.91 functional polysiloxane of Example BCarbamate- — — — — — — — 27.53 — — functional polysiloxane of ExampleC * Comparative examples.¹2-(2H-Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol,ultraviolet light stabilizer available from Ciba-Geigy Corp. ²Stericallyhindered amino ether light stabilizer available from Ciba-Geigy Corp.³Methylated/butylated melamine formaldehyde resin available fromSolutia, Inc. ⁴Polybutylacrylate, 60 percent solids in xylene.⁵Dodecylbenzenesulfonic acid, 70 percent solids in isopropanol.⁶Dodecylbenzenesulfonic acid, 91% total neutralization withdiisopropanolamine, 40% acid solids in ethanol. ⁷Carbamate functionalacrylic resin prepared as follows: A suitable reaction flask equippedfor vacuum distillation was flushed with N₂ and 1670.2 g of 88% acrylicpolyol solution, (40% HPA, 60% BMA), in 1-methoxy-2-propanol, 4.9 g ofbutyl stannoic acid and 4.9 g triphenyl phosphite added. The reactionwas placed under vacuum and heated to a temperature of 140° C. To theresulting mixture was added, over a period of 3 hours, 1263.64 # g of a38% solution of 1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol.The resulting distillate was collected. After the addition wascompleted, the temperature was increased to 150° C. and held at thattemperature until distillation had stopped. The reaction was cooled to90° C. and brought to atmospheric pressure. The resulting resin had ahydroxyl value of 34.48 and was diluted with a mixture of 251.4 g of1-methoxy-2-propanol and 3-ethoxy ethyl propionate.

Each of the above coating compositions of Examples 1 through 10 wasprepared as a one-pack coating composition by adding the ingredients inthe order shown and mixing under mild agitation.

Test Panel Preparation:

BWB-5555 black waterborne basecoat (commercially available from PPGIndustries, Inc.) was spray applied to steel panels (4 inches×12 inches)coated with ED5000, cationic electrodepositable primer commerciallyavailable from PPG Industries, Inc. The panels were pre-baked at atemperature of 285° F. for approximately 30 minutes. Each of the coatingcompositions of Examples 1 through 10 above was applied as a transparenttopcoat to the basecoated panels (prepared as described immediatelyabove) using a 6 mil drawdown bar to form thereon a transparent topcoat.The topcoated panels were allowed to flash at ambient temperatures forapproximately 5 minutes, then thermally cured at 285° F. for 30 minutes.The multi-component composite coatings were tested for various physicalproperties including gloss, scratch resistance, hardness and haze.

Test Procedures:

Scratch resistance of coated test panel was measured using the followingmethod: Initial 20° gloss of the coated panels is measured with a 20°NOVO-GLOSS 20 statistical glossmeter, available from Gardner InstrumentCompany, Inc. Coated panels were subjected to scratch testing bylinearly scratching the coated surface with a weighted abrasive paperfor ten double rubs using an Atlas AATCC Scratch Tester, Model CM-5,available from Atlas Electrical Devices Company of Chicago, Ill. Panelswere then rinsed with water and carefully patted dry. The 20° gloss wasmeasured on the scratched area of each test panel. The number reportedis the percent of the initial gloss retained after scratch testing,i.e., 100%×scratched gloss/initial gloss. Post-weathering scratchresistance (retained scratch resistance) was measured using the scratchtest method described above after the unscratched test panels weresubjected to simulated weathering by QUV exposure to UVA-340 bulbs in aweathering cabinet available by Q Panel Co. Testing was as follows acycle of 70° C. for 8 hours followed by 50° C. for 4 hours (totalexposure time of 100 hours). The number reported is the percent of theinitial gloss retained after post-weathering scratch testing, i.e.,100×post-weathering scratched gloss/initial gloss.

Film hardness of the multi-layer composite coatings was measured using aTUKON Hardness Tester according to ASTM-D1474-92 to give Knoop Hardnessvalues. Higher reported values indicate harder coating surfaces.

The degree of haziness or lack of film clarity of the transparenttopcoat was measured using BYK HAZE/GLOSS instrument from BYK Chemical.Higher numbers indicate a higher degree of haziness or lack of clarity.Test results are provided in the following Table 1.

TABLE 1 % Initial 20° Gloss Retained % Initial 20° Post- 20° Gloss AfterWeathering Ex- Gloss Mar/Scratch Mar/Scratch Knoop ample (Initial) TestTest Hardness Byk Haze 1 89 26% 25% 10.9 14 2 89 58% 30% 12.1 18 3 8882% 86% 11.2 19 4 50 82% 62% 12.1 294 Haze 5 89 85% 28% 11.8 19 6 87 95%94% 12.1 14 7 89 80% 22% 11.9 14 8 91 69% 31% 10.9 14 9 88 95% 93% 11.214 10 86 97% 92% — —

The results reported in Table 1 above illustrate that themulti-component composite coating compositions of the invention ofExamples 4-10 provide coatings with good Knoop film hardness and initialand retained scratch resistance after simulated weathering testing.

Examples 11-18

The following describes the preparation of coating compositions preparedas two-pack systems, that is, a polyisocyanate curing agent was added tothe remaining ingredients just prior to application. The two-packsystems were prepared from a mixture of the ingredients listed below.Amounts indicated for each component are expressed in grams totalweight.

Example Example Example Example Example Example Example ExampleIngredients 11* 12* 13* 14* 15 16 17 18 Methyl amyl ketone 20.0 20.020.0 20.0 20.0 20.0 20.0 40.0 Acrylic polyol¹ 89.6 89.6 89.6 89.6 43.343.3 43.3 CYMEL 202² — — 18.8 18.8 18.8 18.8 18.8 18.8 Acid catalyst³ — 1.3 —  1.3 —  1.3  1.3  1.3 Polysiloxane polyol — — — — 23.4 23.4 20.913.4 or Example 4 Silica dispersion⁴ — — — — — —  7.7 30.8 DESMODUR N-41.4 41.4 24.8 24.8 33.3 33.3 33.3 33.3 3390⁵ *Comparative examples.¹(18% butyl methacrylate/40% hydroxy-propylmethacrylate/1% methylmethacrylate/20% styrene/19% butyl acrylate/2% acrylic acid) 71% solidsin a solvent blend of (55% xylene/45% aromatic hydrocarbon). ²Highimino, methylated/butylated melamine formaldehyde resin available fromCytec Industries, Inc. ³Phenyl acid phosphate solution, 75 percent inisopropanol. ⁴Silica Dispersion of Example DD ⁵Polyisocyanate based onhexamethylene diisocyanate available from Bayer Corporation.

TABLE 2 % Initial 20° Gloss Retained % Initial 20° Post- Initial GlossAfter Weathering Ex- 20° Mar/Scratch Mar/Scratch Knoop ample Gloss TestTest Hardness Byk Haze 11 88 17% 22% 10.9 11 12 88 15% 19% 10.0 11 13 9030% 21% 10.9 10 14 92 57% 48% 13.9 11 15 88 47% 14% 10.0 14 16 89 88%66%  9.8 15 17 86 98% 97% 11.8 18 18 84 98% 98% 10.5 18

The data presented in Table 2 above illustrate that the coatingcompositions of Examples 15-18 of the present invention exhibit goodinitial and retained scratch resistance properties after simulatedweathering.

Example 19

This example describes the preparation of a one-component coatingcomposition used to form the transparent topcoat in a multi-componentcomposite composition of the present invention suitable for applicationto a flexible elastomeric substrate. The film forming compositioncontains a hydroxyl functional group-containing polysiloxane andinorganic particles in the form of a colloidal silica. The coatingcomposition was prepared from a mixture of the following ingredientsunder agitation in the order which they appear:

Resin Silica Weight in Ingredients Solids Solids Grams 2-Methoxy propylacetate 2.7 Methyl amyl ketone 40.0 TINUVIN 928 3.0 3.0 TINUVIN 123 0.50.5 Carbamate functional acrylic¹ 21.5 33.6 Carbamate functionalpolyester² 21.5 30.7 Carbamate functional polyether³ 10.0 10.3 Silicadispersion⁴ 7.0 3.0 12.8 RESIMENE 757 40.0 41.2 Flow additive ofComparative 0.3 0.5 Example 1 Catalyst solution⁵ 1.0 2.5 ¹Carbamatefunctional acrylic resin prepared as follows: To a suitable flask wasadded 3652.5 g of 90% acrylic polyol solution (40% HPA, 58% BMA, 2%methyl styrene dimer) in 1-methoxy-2-propanol, 2836.2 grams of a 38%solution of 1-methoxy-2-propyl carbamate in 1-methoxy-2-propanol, 25.0grams of 1-methoxy-2-propanol, 9.6 grams triphenyl phosphite, and 2.4grams butyl stannoic acid. The materials were mixed and then transferredover a period of # 7.3 hours into a reactor vessel suitable for vacuumdistillation. During the transfer, the temperature of the reactor washeld between 131° C. and 139° C., and reduced pressure was maintained toensure steady distillation of 1-methoxy-2-propanol. Upon completion ofthe transfer, pressure was gradually reduced to maintain distillationuntil a final pressure of 41 mm Hg was reached. When distillation wascompleted, the resulting resin was cooled and thinned # with 925 g1-methoxy-2-propanol and 950 g ethyl 3-ethoxypropionate. Prior tothinning, the resin had a measured hydroxyl value of 40.8. Afterthinning, the resin had a measured solids content of 63%, a weightaverage molecular weight of 9107, and a number average molecular weightof 3645 as determined by gel permeation chromatography vs. a polystyrenestandard. ²Carbamate functional polyester prepared as follows: Apolyester was prepared from2,2,4-trimethyl-1,3-pentanediol/trimethylolpropane/neopentyl/glycol/hexahydrophthalicanhydride (22.7/10.6/17.5/49.2 weight ratio) with a resulting hydroxylvalue of 146 and at 100% solids. To a reactor equipped with athermocouple, overhead stirrer, nitrogen inlet, and reflux condenser #was added 375.1 parts by weight of the polyester as prepared immediatelyabove, 71.9 parts methyl carbamate, 1.0 parts butyl stannoic acid, 0.8parts triphenyl phosphite, and 35.0 parts 2-methoxy-1-propanol. Thereactants were heated to reflux under nitrogen blanket at 141° C. andheld for 1 hour. Then, the reflux condenser was removed and the reactorequipped for distillation at atmospheric pressure. The temperature wasgradually increased to 151° C. until # 28.7 parts of distillate werecollected. The mixture was then cooled to 145° C. and the reactorequipped for vacuum distillation. Distillation continued under reducedpressure until 60 mmHg was attained. A total distillate of 78.3 partswas collected. The resulting resin hydroxy value was 33.8 at 100%solids. The resin was cooled and diluted with 140 parts2-methoxy-1-propanol. The final resin solution was 72.2% solids with aweight average molecular weight of # 2197 and number average molecularweight of 1202 as determined by gel permeation chromatography usingpolystyrene standards. ³Polyester of Example B of U.S. Pat. No.5,663,244. ⁴Silica dispersion prepared as follows: a 4-neck reactionflask equipped for vacuum distillation was flushed with N₂. To thereaction flask was added 1051.1 g of siloxane polyol from Example A,1125.8 g of ORGANOSILICASOL MT-ST-M colloidal silica from NissanChemicals and 480.3 g of methyl amyl ketone. The resulting mixture wasvacuum distilled at 25° C. for 4 h. ⁵Solution of 72.9 g dodecylbenzenesulfonic acid/27.1 g diisopropanol amine/51.1 g ethanol/31.2 gisopropanol.

Example 20

This example describes the preparation of a two-component coatingcomposition used to form a transparent topcoat in a multi-componentcomposite composition of the present invention. The film formingcomposition contains both aminoplast and polyisocyanate curing agents,hydroxyl functional group-containing polysiloxane and inorganicparticles in the form of a colloidal silica. The coating composition wasprepared from a mixture of the following ingredients under agitation inthe order which they appear:

Resin Silica Weight in Ingredients Solids Solids Grams Methyl amylketone 35.0 Ethyl 3-ethoxy propionate 11.9 Silica dispersion of Example19 4.7 2.0 8.6 TINUVIN 928 3.0 3.0 CYMEL 202 15.0 18.8 Acrylic polyol¹23.6 47.2 Polyester polyol² 20.3 25.3 Polysiloxane of Example A 10.410.4 TINUVIN 292³ 0.5 0.5 Flow additive of Example 1 0.3 0.5 Thefollowing two ingredients were added to the above mixture immediatelyprior to application of the coating: DESMODUR N-3390 26.0 28.9 Catalystof Example 12 1.0 1.3 ¹Acrylic polyol: (34.8% HEMA/23.4% 2-EHMA/20.8%2-EHA/20% Styrene/1% MAA), 51% in 1:1 xylene/butyl acetate, having aweight average molecular weight of 7200, a number average molecularweight of 2850 based on gel permeation chromatography using polystyrenestandards. ²Polyester polyol: (32% 4-methyl hexahydrophthalicanhydride/22.9% 1,6 hexane diol/18.6% trimethylol propane/18.4% adipicacid/8.1% trimethyl pentane diol), 80% in 60:40 butyl acetate/Solvesso100, having a hydroxy value of 145 and a Gardner-Holte viscosity of X-Z.³Hindered amine light stabilizer available from Ciba-Geigy Corp.

Test Panel Preparation:

MPP4100D, high solids adhesion promoter commercially available from PPGIndustries, Inc., was applied to SEQUEL 1440 TPO plaques, commerciallyavailable from Standard Plaque (4 inches×12 inches), by hand spraying ata dry film thickness of 0.15 mils to 0.25 mils (3.8 microns to 6.4microns). Each Sequel 1440 plaque was cleaned with isopropyl alcoholprior to being treated. The treated Sequel 1440 plaques were allowed tostand for one day before a solventborne black basecoat commerciallyavailable from PPG Industries, Inc., either CBCK8555A (used inconjunction with 2K clearcoats) or CBC8555T (used in conjunction with 1Kclearcoats), was applied at a dry film thickness of 0.8 mils to 1.0 mils(20.3 microns to 25.4 microns). CBCK8555A and CBC8555T basecoats wereapplied by spraymation in two coats with a 90 second Aflash-dry” periodat ambient temperatures between each coat. The basecoated panels wereflash-dried at ambient temperature for 90 seconds before the transparenttopcoats described in the above Examples 19 and 20 were applied byspraymation in two coats with a 90 second ambient flash between eachcoat. The transparent topcoats had a dry film thickness ranging from 1.6mils to 1.8 mils (40.6 microns to 45.7 microns). The topcoated panelswere flashed-dried at ambient temperature for 10 minutes and thenthermally cured at 254° F. (123.3° C.) for 40 minutes. The coated testpanels sat at ambient temperature for four days prior to testing.

The test panels prepared as described immediately above were evaluatedfor 20° gloss, scratch resistance and post-weathering scratch resistanceusing the methods described above for these properties versus commercialone-pack and two-pack systems.

Additionally, the coated test panels were tested for flexibility at 70°F. (21.1° C.). For flex testing, a 1-inch by 4-inch piece was cut fromthe coated test panel. The piece was subjected to a mandrel bend using a2 inch diameter steel mandrel, such that the two ends of the 4-inch longtest piece contacted one another. The test panels were then rated forflexibility by visual inspection for coating cracking on a scale of 0 to10. A “10” rating is recorded where there is no visible paint cracking;a “9” rating has less than five interrupted short line cracks; an “8”has interrupted line cracks with a maximum of four uninterrupted linecracks; a “6” has five to ten uninterrupted line cracks; a “4” has morethan 15 uninterrupted line cracks; and a “0” represents fracture of thesubstrate.

Test results are reported in the following Table 3.

TABLE 3 % Initial 20° % Initial 20° 20° gloss retained gloss retainedGloss after mar/ post- Flexibility EXAMPLE (Initial) scratch testweathering Rating Example 19 86 83 55 8 *Commercial 88 46 11 8 Flexible1K Clear¹ Example 20 85 69 35 10  *Commercial 87 17  8 9 Flexible 2KClear² *Comparative examples. ¹UDC-1000 flexible 1-component clearcoatavailable from PPG industries, Inc. ²TKU-2000 flexible 2-componentclearcoat available from PPG Industries, Inc.

The data presented in Table 3 above illustrate that the coatingcompositions of Examples 19 and 20 of the present invention, whenapplied to thermoplastic polyolefin (TPO) elastomeric substrates,provide similar initial gloss and flexibility properties compared tocommercial clearcoats without silica or polysiloxane, while providingsuperior post-weathering scratch resistance.

Example 21

This example describes the preparation of epoxy/acid coatingcompositions which contain both a functional group-containingpolysiloxane and inorganic particles in the form of colloidal silica atlevels lower than 1% based on total weight of resin solids in thecompositions. The coating compositions were prepared from a mixture ofthe following ingredients:

Ex- Ex- ample ample Example Example Example 21A* 21B* 21C 21D 21EIngredients: (grams) (grams) (grams) (grams) (grams) Methyl amyl 40.040.0 40.0 40.0 40.0 ketone CYMEL 202 2.50 — — — — Silica dispersion¹ — —0.03 0.08 0.17 CYLINK 2000² — 28.30 28.30 28.30 28.30 Polybutylacrylate0.50 0.50 0.50 0.50 0.50 N,N-dimethyl 0.30 0.30 0.30 0.30 0.30 dodecylamine Acrylic resin³ 87.89 87.89 87.89 87.89 87.89 Crosslinker⁴ 63.6963.69 63.69 63.69 63.69 Catalyst of — 1.30 1.30 1.30 1.30 Example 12*Comparative examples. ¹30% by weight on solilds Nissan MT-ST colloidalsilica dispersed in the polysiloxane polyol of Example A.²Tris(alkylcarbamoyl)triazine crosslinker (TACT), available from CYTECIndustries, Inc. ³Epoxy functional acrylic resin prepared from 50%glycidyl methacrylate, 40.8% butyl methacrylate, 7% styrene, 0.2% methylmethacrylate, and 2% methyl styrene dimer; 60% solids in xylene. ⁴Acidfunctional crosslinker prepared from 17 weight percent pentaerythritoland 83 weight percent methyl-hexahydrophthalic anhydride.

The coating compositions of Examples 21A-21E were applied over a blackbasecoat (OBISIDIAN SCHWARTZ basecoat, available from PPG Industries,Inc,) which had been previously applied to the test panels and cured for30 minutes at 285° F. (140.6° C.). The transparent coating compositionof each example was drawn down over the cured basecoat using a 6 milsquare drawdown bar and cured for 30 minutes at 285° F. (140.6° C.).

TABLE 4 Post-Mar Post-weathering Initial 20° % 20° Gloss scratch (mar)Example Gloss Retained % 20° Gloss Retained  21A* 84 14 12  21B* 86 2723 21C 86 49 42 21D 86 67 58 21E 85 80 68

The data presented in Table 4 above illustrate that the coatingcompositions of Examples 21C-21E of the present invention providesuperior initial and retained mar resistance when compared tocomparative compositions which contain no inorganic particles orpolysiloxane.

Example 22

This example describes the preparation of two-component coatingcompositions 22A through 22I which illustrate the effects of lower(i.e., ≦2 weight percent) levels of polysiloxane. Comparative Examples22A and 22B contain 0% colloidal silica/0% polysiloxane and 2% colloidalsilica/0% polysiloxane, respectively. Examples 22C-22I describe coatingcompositions which each contain 2 weight % of a polysiloxane.

POLYSILOXANES EVALUATED HYDROXYL SILOXANE EQUIVALENT CODE WEIGHTDESCRIPTION Polysiloxane of 190 Reaction product of pentasiloxaneExample A containing Si—H with trimethylol- propane monoallyl ether KR2001 252 Hydroxy functional methyl and phenyl siloxane from Shin-EtsuChemical Co. BYK 370 1600 Polyester modified hydroxy functionaldimethylpolysiloxane from BYK Chemie BYK 373 701 Polyether modifiedhydroxy functional dimethylpolysiloxane from BYK Chemie BYK 375 1870Polyether-polyester modified hydroxy functional dimethylpolysiloxanefrom BYK Chemie BYK 325 0 Polyether modified methyl alkylpoly- siloxanefrom BYK Chemie BYK 310 0 Polyester modified dimethylpoly- siloxane fromBYK Chemie

Coating Compositions

A coating composition was prepared from a mixture of the followingingredients:

Ingredient Solid Weight (G) Formula Weight (G) Methyl amyl ketone — 31.2CYMEL 202 15.0 18.8 Acrylic polyol¹ 61.5 102.1 Polybutylacrylate 0.3 0.5DESMODUR N-3390 22.4 24.9 Phenyl acid 1.0 1.3 phosphate catalyst¹Copolymer of 39.35 weight % hydroxyethyl methacrylate/57.05 weight %isobutyl methacrylate/1.96 weight % acrylic acid/1.63 weight % methylstyrene dimer, 60.25% solids in a solvent blend.

Each of the coating compositions of Example 22A-22I was prepared byadding the following weight percentages of colloidal silica andpolysiloxane ingredients to 178.8 grams of the coating compositiondescribed immediately above. The coating compositions thus prepared wereapplied and tested as described above for Examples 1-18.

% Initial 20° Gloss Retained % Initial After Coefficient Colloidal %Siloxane 20° Mar/Scratch of Friction Example Silica¹ Siloxane Type GlossTest (μ) 22A 0 0 — 86 38% 0.19 22B 2 0 — 86 44% 0.18 22C 2 1.1Polysiloxane 84 89% 0.17 of Example A 22D 2 1.5 KR-2001 85 51% 0.12 22E2 1.0 Byk-370 85 58% 0.07 22F 2 1.0 Byk-373 Too Seedy To Test 22G 2 1.0Byk-375 76 57% 0.04 22H 2 1.0 Byk-325 Too Seedy To Test 22I 2 1.0Byk-310 84 52% 0.09 ¹ORGANOSILICASOL MT-ST, available from NissanChemicals.

The data reported above illustrate that the coating compositions ofExample 22C of the present invention containing very low levels (i.e.,1.0 weight percent) of the polysiloxane polyol of Example A inconjunction with inorganic particles in the form of colloidal silicaprovide excellent initial scratch (mar) resistance. Further, the dataillustrate that the inorganic particles and the polysiloxane polyol actsynergistically to provide excellent post-weathering scratch resistance.

Example 23

This example describes the preparation of transparent topcoat coatingcompositions which, subsequent to application and cure, were evaluatedusing transmission electron microscopy surface characterizationtechniques. Example 23A describes the preparation of a transparenttopcoat composition of the present invention containing inorganicparticles in the form of colloidal silica in conjunction with thepolysiloxane polyol of Example A, both of which were added as separatecomponents. Comparative Example 23B describes the preparation of acomparative transparent topcoat composition containing inorganicparticles in the form of colloidal silica, but no polysiloxane. Example23C describes the preparation of a transparent topcoat composition ofthe present invention where the inorganic particles in the form ofcolloidal silica were dispersed in the polysiloxane polyol of Example Aprior to incorporation into the composition.

Each of the coating compositions were prepared as described below.

Example 23A

Description Solids Total Weight Methyl Amyl Ketone — 66.6 Tinuvin 9283.0 3.0 Colloidal silica¹ 5.0 16.7 Cymel 202 15.0 18.8 Polysiloxanepolyol of Example A 2.0 2.0 Acrylic polyol² 63.0 106.1 Tinuvin 123 1.01.0 Polybutylacrylate 0.3 0.5 Catalyst of Example 12 1.0 1.3 DesmodurN-3390³ 20.0 22.2 ¹ORGANOSILICASOL MT-ST, available from NissanChemicals. ²Polymerization reaction product prepared from the followingmonomer composition in Dowanol PM acetate, using VAZO 67 (azobis-2,2═-(2-methylbutyronitrile), 4.9% on total monomer charge as aninitiator): 39.4 parts of hydroxyethyl methacrylate, 2 parts of acrylicacid, 57 parts of isobutyl methacrylate, and 1.6 parts ofα-methylstyrene dimer. The polymer solution exhibited the followingproperties: 60% solids contents; 82.4 OH value; molecular weight: 7410(Mw). ³Hexamethylene diisocyanate crosslinker, 90% solids, availablefrom Bayer Corporation

Example 23B

Description Solids Total Weight Methyl Amyl Ketone — 66.2 Tinuvin 9283.0 3.0 ORGANOSILICASOL ® MT-ST 5.0 16.7 Cymel 202 15.0 18.8 Acrylicpolyol of Example 23A 65.7 110.7 Tinuvin 123 1.0 1.0 Polybutylacrylate0.3 0.5 Catalyst of Example 12 1.0 1.3 Desmodur N-3390 19.3 21.4

Example 23C

Description Solids Total Weight Methyl amyl ketone — 25.0 Silicadispersion¹ 6.7 8.6 Tinuvin 928 3.0 3.0 Acrylic polyol² 35.9 65.3Tinuvin 292 0.5 0.5 Polybutylacrylate 0.3 0.5 Polysiloxane polyol ofExample A 15.3 15.3 Cymel 202 15.0 18.8 Catalyst of Example 12 0.5 0.7Desmodur N-3300³ 29.1 29.1 ¹Dispersion of colloidal silica inpolysiloxane prepared as follows: A 4-neck reaction flask equipped forvacuum distillation was flushed with N₂. To the reaction flask was added3151.4 g of polysiloxane polyol of Example A, 4501.9 of colloidal silica(ORGANOSILICASOL MT-ST, available from Nissan Chemicals) and 1440.6 g ofmethyl amyl ketone. The resulting mixture was vacuum distilled. ²VK-114,an acrylic polyol having the following properties: solids 55%, Mw 4000and OH value 101, available from PPG Industries, Inc. ³Hexamethylenediisocyanate crosslinker, 100% solids, available from Bayer Corporation.

Test Panel Preparation for Examples 23A AND 23B:

A black basecoat, SMARAGDSCHWARZ MICA, available from PPG (B&K) Germany,was spray applied to steel test panels (4″×12″ panels commerciallyavailable from ACT Laboratories, Inc. of Hillsdale, Mich.) which hadbeen coated with ED-5000 electrocoat primer and GPXH-5379 primersurfacer (both commercially available from PPG Industries, Inc.) usingspraymation. The basecoat was applied in two coats with a no flashbetween coats followed by a five minute heated flash at 200° F. beforeapplication of the clearcoats. The basecoat had a dry film thickness of0.47 mils (11.75 micrometers). The coating compositions of Examples 23Aand 23B were spray-applied to the cured basecoats in two coats with a60-second flash between coats followed by 5 minute ambient flash priorto curing for 30 minutes at 285° F. (140.6° C.). Each clearcoat had adry film thickness of approximately 2.1 mils (54.5 micrometers).

Test Panel Preparation for Example 23C:

A black basecoat, OBSIDIAN SCHWARTZ, available from PPG (B&K) Germanywas spray applied and cured as described immediately above for Examples23A and 23B. The coating composition of Example 23C was applied to thebasecoat as a clearcoat and cured using the procedure described abovefor the clearcoats of Example 23A and 23B. The basecoat had a dry filmthickness of 0.5 mils (12.5 micrometers) and the clearcoat had a dryfilm thickness of 1.44 mils (36 micrometers).

Cross-Sectional Transmission Electron Microscopy

Cured coating samples were delaminated from the substrate and embeddedin epoxy using an EPONATE 812 epoxy embedding kit available from TedPella's Inc. in a polyester bottle cap mold. Once heat set, samples wereremoved from the molds and were cut using an X-ACTO razor saw, extrafine tooth #75350 to a size of approximately 1.5 centimeters×1centimeter. The sized samples were then microtomed at ambienttemperature using a RMC MY6000XL microtome using a vice clamp specimenholder. Microtome sections were cut using a 452 diamond knife edgemounted in a holder with a water-filled boat cavity. Cuts were made toan interference color of bright to dark gold color (approximately 100nanometers to 150 nanometers), then individual cut specimens werecollected onto a TEM formvar-carbon coated grid. Excess water wasremoved with filter paper and the thin sections were air-dried atambient temperature on a glass microscope slide. Sections were sorted byinterference color thickness. The coating specimens were oriented on theglass slides to permit tilting on axis such that a perpendicularcross-section could be observed. Samples were placed in a Philips CM12TEM operated at a 100 KV accelerating voltage, in transmission mode,using a standard tungsten filament and examined at variousmagnifications for documenting of coating surface morphologies andparticle concentration by visual observation. Kodak SO-163 electronimage film was used to create electron micrograph negatives and thenegatives subsequently developed.

FIG. 1 is an electron micrograph of a transmission electron microscopyimage (30,000× magnification) of a cross-section of a cured transparenttopcoat composition of Example 23A which contains both colloidal silicaand polysiloxane added as separate components. Upon visual inspection,it can be observed that the concentration of particles in the form ofcolloidal silica 1 b at the surface region of the cured composition,that is, a region extending from the exposed air-surface interface 1 ato a cured coating depth of 20 to 50 nanometers (1millimeter=approximately 30 nanometers) below the exposed surface isgreater than the concentration of colloidal silica 1 c within a bulkregion of the cured composition. It should also be noted that theparticles 1 b and 1 c exist as agglomerates dispersed within the polymermatrix, rather than as discrete monodispersed particles.

FIG. 2 is an electron micrograph of a transmission electron microscopyimage (30,000× magnification) of a cross-section of the curedcomparative transparent topcoat coating composition of Example 23B whichcontains colloidal silica but not polysiloxane. Upon visual inspection,it can be observed that the concentration of particles in the form ofcolloidal silica 2 b at the surface region of the comparative curedcomposition, that is, a region extending from the exposed air-surfaceinterface 2 a to a cured coating depth of 20 to 50 nanometers (1millimeter=approximately 30 nanometers) below the exposed surface isless than the concentration of colloidal silica 2 c within a bulk regionof the cured composition. In fact, there is essentially no colloidalsilica observed in the surface region. It should also be noted that theparticles 2 b and 2 c appear as agglomerates within the polymer matrix,rather than as discrete monodispersed particles.

FIG. 3 is an electron micrograph of a transmission electron microscopyimage of a cross-section of the cured transparent topcoat coatingcomposition of Example 23A (see FIG. 1) viewed at a magnification of54,000×.

FIG. 4 is an electron micrograph of a transmission electron microscopyimage (105,000× magnification) of a cross-section of a preferred curedtransparent topcoat coating composition of the present invention whichcontains a pre-formed dispersion of colloidal silica and a polysiloxane.Upon visual inspection, it clearly can be observed that theconcentration of particles in the form of colloidal silica 4 b at thesurface region of the cured composition, that is, a region extendingfrom the exposed air-surface interface 2 a to a cured coating depth of20 to 50 nanometers below the exposed surface, is greater than theconcentration of colloidal silica 4 c within a bulk region of the curedcomposition. It should also be noted that the particles 4 b and 4 cappear as discrete monodispersed particles distributed within thepolymer matrix, rather than as agglomerated particles (compare FIGS. 1and 2).

Example 24

In this example, a coating composition of the present invention whichcontains inorganic particles in the form of colloidal silicapre-dispersed in a functional group-containing polysiloxane wasevaluated versus a comparative commercial two-component isocyanateclearcoat for coating penetration (scratch depth) as a function of loadand scratch distance.

Example 24A

A coating composition of the present invention was prepared from amixture of the following ingredients:

Total Weight Ingredient Solids (grams) Methyl amyl ketone — 25.0 Silicadispersion¹ 6.7 8.6 TINUVIN 928 3.0 3.0 Acrylic polyol of Example 23C40.9 74.4 TINUVIN 292 0.5 0.5 Polybutylacrylate flow additive 0.3 0.5Polysiloxane polyol of Example A 10.3 10.3 CYMEL 202 15.0 18.8 Catalystof Example 12 0.5 0.7 DESMODUR N-3300 29.1 29.1 ¹A proportional scaledbatch of Example 23C.

Example 24B

A black waterborne basecoat was prepared from a mixture of the followingingredients:

Solids Total Weight Ingredients (grams) (grams) PROPASOL B¹ — 45.0 CYMEL327² 35.0 38.9 TINUVIN 1130³ 3.2 3.2 Phosphated epoxy⁴ 0.5 0.8Dimethylethanolamine (50% in water) — 2.0 Latex⁵ 46.5 109.4 Mineralspirits — 8.0 Water-reducible urethane⁶ 10.0 42.6 Black pigmentdispersion⁷ 11.5 47.6 Dimethylethanolamine (50% in water) — 1.0Deionized water — 57.5 ¹N-Butoxypropanol available from ChemcentralCorporation, Chicago. ²Methylated melamine-formaldehyde resin availablefrom Cytec Corporation. ³Substituted hydroxyphenyl benzotriazoleultraviolet light stabilizer available from Ciba Geigy Corporation.⁴Proprietary phosphatized epoxy resin (EPON 828 from Shell ChemicalCompany) from PPG Industries, Inc. ⁵Proprietary acrylic-polyester latexfrom PPG Industries, Inc. ⁶Proprietary waterborne polyurethane, PPGIndustries, Inc. ⁷Proprietary carbon black dispersion in waterdispersible acrylic resin, PPG Industries, Inc.

Test Panel Preparation:

Steel substrate test panels (available from ACT Laboratories, Inc.) werecoated with ED-5000 electrocoat primer (available from PPG Industries,Inc.). The basecoat of Example 24B above was spray applied to the primedpanels in two successive coats with no flash period between coats. Thebasecoated panels were flash-heated for 5 minutes at 200° F. prior toapplication of the clearcoats. Basecoat dry film thickness was 0.4 mils(10 micrometers). The coating composition of Example 24A above and acommercial two-component clearcoat (TKU-1050 available from PPGIndustries, Inc.) were spray applied to the basecoated panels in twocoats with a 60-second flash between coats, followed by a 10-minuteambient flash before curing for 30 minutes at 285° F. (140.6° C.).Clearcoat dry film thickness was 1.6 mils for each example (40micrometers).

The test panels prepared as described above were tested by MTSCorporation of Oak Ridge, Tenn. for surface penetration (or scratchdepth) as a function of load applied at a given rate over a givendistance. The Nano Indenter XP system was employed using a cube cornerindenter, at a scratch velocity of 20 μm/s, using normal load ramp of1000 μN/s to a maximum load of 25 mN over a scratch length of 500 μm.

FIG. 5 is a graph (scratch depth versus scratch distance) of coatingsurface penetration relative to load for the commercial two-componentpolyurethane coating (comparative example) using nano-indentertechniques described above. Critical load determined for thiscomposition is 5.62 mN. As used herein, the term “critical load” isdefined from the onset of catastrophic cracking, i.e., failure of thecoating.

FIG. 6 is a graph (scratch depth versus scratch distance) of coatingsurface penetration relative to load for the two-component coating ofExample 24A of the present invention described above using thenano-indenter techniques described above. Critical load determined forthe composition of the invention is 11.74. The coating composition ofthe present invention required a greater force to bring about coatingfailure than did the commercial control under the same test conditions.

Example 25

This example describes the preparation of a series of coatingcompositions of the present invention (Examples 25B-25G) which containincreasing amounts of particles in the form of colloidal silica.Comparative example 25A describes a coating composition which containsno particles. The test results in the following Table 5 illustrate theeffect of silica loading on post-weathering scratch resistanceproperties of the cured coating compositions.

Coating Composition Without Inorganic Particles

A coating composition was prepared by mixing under mild agitation thefollowing components: 35.9 weight percent of the acrylic polyol ofExample 23C; 29.1 weight percent DESMODUR N-3300; 20 weight percent ofthe siloxane polyol of Example A (this amount includes the siloxanepolyol incorporated in the form of the silica dispersion); 15 weightpercent CYMEL 202; 3 weight percent TINUVIN 98, 0.3 weight percentpolybutylacrylate flow additive, and 0.5 weight percent of the catalystof Example 12, where weight percentages were based on weight of totalresin solids of the coating composition. Particles were incorporated atlevels ranging from 0 to 8.5 weight percent into the compositiondescribed immediately above in the form of the colloidal silicadispersion of Example 19.

The compositions of Examples 25A-25G were applied to test panels asdescribed above for Example 24. The coated panels were subsequentlytested for initial and post-weathering scratch resistance properties asdescribed above. Test results are reported below in the following Table5.

TABLE 5 Scratch Resistance Initial Scratch After 148 Hours QUVResistance 20° Gloss Exposure 20° Gloss Example % Initial Initial 25Silica** Retained % Gloss Retained % Gloss  A* 0 88 79% 89 51% B 0.25 8889% 86 90% C 0.5 86 95% 88 91% D 1.0 86 95% 87 93% E 2.0 85 93% 86 95% F4.0 85 91% 86 95% G 8.5 86 88% 87 95% *Comparative example. **Percent byweight based on weight of total resin solids in the composition ofsilica incorporated in the form of the silica dispersion of aproportionally scaled batch of Example 23C.

The test data reported above in Table 5 illustrate the significantimprovement in post-weathering scratch resistance attained byincorporating even low levels (e.g. 0.25%) of silica in the coatingcompositions of the invention. Further, the data illustrates thatinitial and post-weathering scratch resistance results obtained usingcoating compositions having low levels of silica (i.e., 2.0% or less)are similar to those results obtained using coating compositions havinghigher levels of silica. FIGS. 7 and 8 are electron micrographs of atransmission electron microscopy image (105,000× magnification) of across-section of the coating composition according to Example 25E, andFIGS. 9 and 10 are electron micrographs of a transmission electronmicroscopy image (105,000× magnification) of a cross-section of thecoating composition according to Example 25G.

Example 26

This example describes the preparation of several coating compositionsof the present invention (Examples 26B-26D) which are in solidparticulate form. The compositions of Examples 26C and 26D containinorganic particles in the form of aluminum oxide. In the composition ofExample 26C, the aluminum oxide particles have been dispersed in asurface active agent and in the composition of Example 26D, the aluminumoxide particles have been dispersed in the polysiloxane polyol ofExample A. The compositions of Comparative Examples 26A and 26B eachcontain a surface active agent but no aluminum oxide. Each of thecompositions was prepared by blending the components listed below in aHenschel Blender for 60 to 90 seconds and subsequently extruding themixtures through a Werner & Pfeider co-rotating twin screw extruder at ascrew speed of 450 rpm and an extrudate temperature of 100° C. to 125°C. (212° F. to 257° F.). Each of the extruded compositions was thenground to a particle size of 14 to 27 microns using an ACM Grinder (AirClassifying Mill from Micron Powder Systems of Summit, N.J. to form apowder coating composition. Each powder coating composition waselectrostatically spray applied to test panels and evaluated for scratchresistance properties (as described below). Amounts listed belowrepresent parts by weight.

Example Example Example Example Ingredients 26A 26B 26C 26D Epoxyfunctional acylic¹ 69.05 69.05 68.98 49.11 Dodecanedioic acid 22.6822.68 22.65 22.04 Benzoin 0.20 0.20 0.20 0.20 WAX C MICRO- 0.60 0.600.60 0.60 POWDER² TINUVIN 144³ 2.00 2.00 2.00 2.00 CGL-1545⁴ 2.00 2.002.00 2.00 HCA-1⁵ 2.00 2.00 2.00 2.00 ARMEEN M2C⁶ 0.37 0.37 0.37 0.37Surface active agent A⁷ — 1.10 — — Surface active agent B⁸ 1.10 — — —Aluminum oxide — — 1.20 — dispersion A⁹ Aluminum oxide — — — 20.58dispersion B¹⁰ Total 100.00 100.00 100.00 100.00 ¹Glycidyl methacrylatefunctional acrylic polymer prepared as described in PCT PatentPublication WO 97/29854 and PCT patent application Ser. No. US97/16800,having a number average molecular weight (“Mn”) range of 1000 to 5500; arange of glass transition temperature (Tg) of 30° C. to 60° C. asmeasured or 50° C. to 85° C. as calculated by the Acrylic GlassTransition Temperature Analyzer from Rohm and Haas Company, based on theFox equation; and a # range of epoxy content ranging from 35 to 85weight percent of the monomers to prepare the epoxy acrylic polymer. ²Afatty acid amide (ethylene bis-stearoylamide) available fromHoechst-Celanese.³2-tert-butyl-2-(4-hydroxy-3,5-di-tert-butylbenzyl)[bis(methyl-2,2,6,6,-tetramethyl-4-piperidinyl)]dipropionate,an ultraviolet light stabilizer available from Ciba-Geigy Corp.⁴2-[4((2-Hydroxy-3-(2-ethylhexyloxy)propyl)-oxy]-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,an ultraviolet light stabilizer available from Ciba-Geigy Corp.⁵Oxaphosphone oxide, an anti-yellowing agent available from SankoChemical Corp. ⁶Methyl dicocoamine available from Akzo Nobel Corp.⁷Prepared by solution polymerization in xylene of the followingmonomers: 73.5% 2-ethyl hexyl acrylate, 23.5% ethyl acrylate and 3%methacrylic acid. Polymerization was carried out at reflux temperaturein the presence of di-t-amyl peroxide and t-butyl peracetate. Thesurface active agent was then vacuum stripped to 100% resin solids.⁸Prepared by solution polymerization in xylene and toluene of thefollowing monomers: 81.2% 2-ethyl hexyl acrylate, 11.8% hydroxyl ethylacrylate and 7% N,N-dimethylaminoethyl methacrylate. Polymerization wascarried out at reflux temperature in the presence of VAZO 67(2,2=-Azobis-(2-methylbutyronitrile)). The surface active agent was thenvacuum stripped to 100% resin solids. ⁹Fumed aluminum oxide (availableas ALUMINUM OXIDE C from Degussa-Huls Corporation) dispersed 10% in thesurface active agent A described above. ¹⁰Fumed aluminum oxide(described above) dispersed in the polysiloxane polyol of Example A,then blended in the glycidyl methacrylate functional acrylic describedabove (87.5% acrylic/2.43% aluminum oxide/10.07 siloxane polyol).

The powder coating compositions of Examples 26A-26D wereelectrostatically spray applied to test panels which were previouslycoated with an electrodepositable primer (commercially available asED5051 from PPG Industries, Inc. of Pittsburgh, Pa.). The powder coatingcompositions were applied at film-thickness of 2.3 to 2.8 mils (58 to 71micrometers) and cured for a period of 30 minutes at a temperature of293° F. (145° C.). The resulting coated panels were evaluated forinitial 20° gloss as described above. The coated panels were then testedfor scratch (mar) resistance properties using an Atlas Mar Tester andthe following procedure. Using a felt cloth clamped to the acrylicfinger on the arm of the instrument, a set of ten double rubs was run oneach coated panel to which BON AMI cleanser had been applied. Each ofthe tested panels was washed with cool tap water and thoroughly dried.The marred surface of each tested panel was then re-evaluated for 20°gloss. Scratch (mar) resistance test results are expressed as thepercentage of the 20° gloss retained after the surface is marred. Thatis, Scratch (mar) Resistance=(Marred 20° gloss/Initial 20° gloss)×100.The test data presented below in the following Table 6 is reported incomparative form, i.e., the results for Examples 26B to 26D are comparedwith test results for the control composition of Example 26A. A “+”indicates an improvement in scratch (mar) resistance properties over thecontrol composition.

TABLE 6 Scratch (mar) Resistance Rating Comparative Example A ControlExample B + Example C ++ Example D 0

The mar resistance testing data presented in Table 6 illustrate theimprovement in scratch (mar) resistance provided by the inclusion inpowder coating compositions of particles in the form of aluminum oxideparticles.

Example 27

A coating composition of the present invention was prepared from amixture of the following ingredients:

Resin Total Weight Ingredients Solids (%) (Grams Methyl Amyl Ketone —45.0 Tinuvin 928 3.0 3.0 Silica dispersion of Example 23C 4.67 8.8Polysiloxane polyol of Example A 10.33 10.33 Cymel 202 15.0 18.75Acrylic polyol of Example 23C 43.10 69.68 Tinuvin 292 0.5 0.5 Catalystof Example 12 0.5 0.67 DESMODUR N3300 23.4 23.4 DESMODUR Z4470 3.5 5.0

A basecoat, Azuritblau, available from PPG (B&K) Germany was applied toprimed steel automotive substrate. The basecoat was built to a filmthickness ranging from between 12 and 15 microns, followed by a fiveminute heated flash at 80° C. before application of the coatingcomposition of Example 27. The coating composition of Example 27 wasspray-applied wet-on-wet to the basecoat to build a film thickness ofthe clearcoat ranging from between 35 and 45 microns. The coating wasthen cured 30 minutes at 130° C.

Example 28

Silylated compounds for use in the coating compositions disclosed belowwere prepared as follows:

Silylated Compound Resin A

This example illustrates the preparation of a silylated compound that isa half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

A reaction vessel equipped with stirrer, thermocouple, temperaturecontrol, pumps and fitted with valved ports was charged with 1202.9grams trimethylolpropane (commercially available from Bayer USA), 14.4grams of triphenyl phosphine (commercially available from Aldrich®),12.1 grams of triisooctyl phosphite (commercially available from GESpecialty Chemicals), and 800.0 grams of n-butyl acetate (commerciallyavailable from Union Carbide Chemicals and Plastics Co., Inc.).

The reactor was heated to 115° C. and 4436.7 grams ofmethylhexahydrophthalic anhydride (commercially available from MillikenChemical) were added over 90 minutes, and then held 4 hours at 115° C.1533.4 grams of propylene oxide (commercially available from FisherScientific Company) was charged to the reactor over 1 hour. The reactionwas held 4 hours until the acid value was less 5.38 mg KOH/gram.Residual propylene oxide was removed by vacuum distilling at 60 to 80 mmHg at 96° C. max. The resultant product had a total solids content of95.25%.

This product was silylated by the following procedure: 637.6 grams(95.25% solids) of the previously described material were charged to areaction flask equipped with an overhead stirrer, nitrogen inlet,thermocouple, addition funnel, and condenser. The temperature wasincreased to 110° C. for one hour with nitrogen sparge to ensure thatthe system was dry. The temperature was then decreased to 85° C. undernitrogen blanket, at which time 180.9 grams hexamethyldisilazane(commercially available from Aldrich®) were added drop-wise over a 30minute period. The reaction was allowed to continue one additional hour,at which time a nitrogen sparge was introduced. The reaction wasconsidered complete when the size of the IR peak corresponding to thehydroxyl moiety was negligible. The solution was allowed to continuestirring under nitrogen sparge at 85° C. until the ammonia (by-product)was removed. Theoretical resin solids content was 96.3%.

Silylated Compound Resin B

This example illustrates the preparation of a silylated compound that isa half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

A reaction vessel equipped with stirrer, thermocouple, temperaturecontrol, pumps and fitted with valved ports was charged with 550.0 gramstrimethylolpropane (commercially available from Bayer USA), 6.8 grams oftriphenyl phosphine (commercially available from Aldrich®), 5.57 gramsof triisooctyl phosphite (commercially available from GE SpecialtyChemicals), and 205.7 grams of n-butyl acetate (commercially availablefrom Union Carbide Chemicals and Plastics Co., Inc.). The reaction washeated to 115° C. 2030 grams of methylhexylhydrophthalic anhydride(commercially available from Milliken Chemical) was added over 90minutes. The reaction was held 4 hours at 115° C. The reactor was cooledto 100° C. and 769.9 grams of propylene oxide (commercially availablefrom Fisher Scientific Company) was added over 1 hour. The reaction washeld 5 hours at 100° C. until the acid value was 3.1 mg KOH/gram.Residual propylene oxide was removed by vacuum distilling at 60 to 80 mmHg at 70C. The resultant product had a total solids content of 95.08%.The product was thinned to 80.0% solids with butyl acetate.

This product was silylated by the following procedure: 3449.3 grams(80.0% solids) of the previously described material were charged to areaction flask equipped with an overhead stirrer, nitrogen inlet,thermocouple, addition funnel, and condenser. The temperature wasincreased to 110° C. for one hour with nitrogen sparge to ensure thatthe system was dry. The temperature was then decreased to 85° C. undernitrogen blanket, at which time 821.9 grams hexamethyldisilazane(commercially available from Aldrich®) were added drop-wise over a onehour period. The reaction was allowed to continue 15 additional hours,at which time a nitrogen sparge was introduced. The reaction wasconsidered complete when the size of the IR peak corresponding to thehydroxyl moiety was negligible. The solution was allowed to continuestirring under nitrogen sparge at 85° C. until the ammonia (by-product)was removed. Theoretical resin solids content was 96.3%.

A silica dispersion, polysiloxane polyol and composition pre-mixturesfor use in the coating compositions disclosed below were prepared asfollows:

Silica Dispersion

The colloidal silica dispersion was prepared from a proportionaly scaledbatch of the silica dispersion of Example 23C.

Polysiloxane Polyol

The polysiloxane polyol was a product of the hydrosilylation of areactive silicone fluid with an approximate degree of polymerization of3 to 7, i.e., (Si—O)₃ to (Si—O)₇. The polysiloxane polyol was preparedfrom a proportionately scaled-up batch of the following mixture ofingredients in the ratios indicated:

Equivalent Parts By Weight Ingredients Weight Equivalents (kilograms)Charge I: Trimethylolpropane 174.0 756.0 131.54 monoallyl ether ChargeII: MASILWAX BASE¹ 156.7² 594.8 93.21 Charge III: Chloroplatinic acid 10ppm Toluene 0.23 Isopropanol 0.07 ¹Polysiloxane-containing siliconhydride, commercially available from BASF Corporation. ²Equivalentweight based on mercuric bichloride determination.

To a suitable reaction vessel equipped with a means for maintaining anitrogen blanket, Charge I and an amount of sodium bicarbonateequivalent to 20 to 25 ppm of total monomer solids was added at ambientconditions and the temperature was gradually increased to 75° C. under anitrogen blanket. At that temperature, 5.0% of Charge II was added underagitation, followed by the addition of Charge II, equivalent to 10 ppmof active platinum based on total monomer solids. The reaction was thenallowed to exotherm to 95° C. at which time the remainder of Charge IIwas added at a rate such that the temperature did not exceed 95° C.After completion of this addition, the reaction temperature wasmaintained at 95° C. and monitored by infrared spectroscopy fordisappearance of the silicon hydride absorption band (Si—H, 2150 cm⁻¹).

Composition Pre-Mixtures

The following pre-mixtures of selected components of the coatingcompositions discussed below were prepared by sequentially mixing eachof the components with agitation.

Total weight Ingredient (grams) Solid weight (grams) Pre-Mix 1: Methyln-amyl ketone 18.0 — Butyl Cellosolve ® acetate¹ 18.0 — Butyl Carbitol ®acetate² 4.0 — TINUVIN 384³ 1.58 1.50 TINUVIN 400⁴ 1.76 1.50 TINUVIN292⁵ 0.40 0.40 Silica Dispersion from above 13.2 10.0 RESIMENE 757⁶ 27.126.3 LUWIPAL 018⁷ 11.9 8.7 ¹2-Butoxyethyl acetate solvent iscommercially available from Union Carbide Corp. ²2-(2-Butoxyethoxy)ethyl acetate is commercially available from Union Carbide Corp.³Substituted benzotriazole UV light stabilizer commercially availablefrom Ciba Specialty Chemicals Corp. ⁴Substituted triazine UV lightstabilizer commercially available from Ciba Specialty Chemicals Corp.⁵Sterically hindered amine light stabilizer commercially available fromCiba Specialty Chemicals Corp. ⁶Methylated and butylatedmelamine-formaldehyde resin available from Solutia Inc. ⁷High imino,butylated melamine formaldehyde resin commercially available from BASFCorp. Pre-Mix 2: Carbamoylated acrylic¹ 79.4 50.0 Carbamoylatedpolyester² 69.4 50.0 ¹(58% butyl methacrylate/40% hydroxypropylacrylate/2% methyl styrene dimer) 64% solids in a solvent blend of (50%DOWANOL PM/50% propanoic acid, 3-ethoxy ethyl ester) 75% carbamoylatedwith methyl carbamate. ²(10.6% trimethylol propane/22.7%2,2,4-trimethyl-1,3-pentanediol/17.5% neopentyl glycol/49.2%hexahydrophthalic anhydride) 69% solids in a solvent blend of (44%DOWANOL PM/56% DOWANOL PM Acetate) 75% carbamoylated with methylcarbamate. Pre-Mix 3: Methyl n-amyl ketone 5.4 — Butyl Cellosolve ®acetate¹ 10.8 — Butyl Carbitol ® acetate² 1.8 — TINUVIN ® 928³ 3.00 3.00TINUVIN ® 292⁴ 0.40 0.40 TINUVIN ® 123⁵ 0.60 0.60 CYMEL ® 1130⁶ 29.929.9 RESIMENE ® 741⁷ 11.3 9.9 ¹2-Butoxyethyl acetate solvent iscommercially available from Union Carbide Corp. ²2-(2-Butoxyethoxy)ethyl acetate is commercially available from Union Carbide Corp.³2-(2H-Benzotriazol-2yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenolUV absorber available from Ciba Specialty Chemicals Corp. ⁴Stericallyhindered amine light stabilizer commercially available from CibaSpecialty Chemicals Corp.⁵Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate hinderedaminoether light stabilizer available from Ciba Specialty ChemicalsCorp. ⁶Methylated and butylated melamine-formaldehyde resin availablefrom Cytec Industries, Inc. ⁷Methylated melamine-formaldehyde resinavailable from Solutia Inc. Pre-Mix 4: Methyl n-amyl ketone 7.5 — ButylCellosolve ® acetate¹ 15.0 — Butyl Carbitol ® acetate² 2.50 — TINUVIN ®928³ 3.00 3.00 TINUVIN ® 292⁴ 0.40 0.40 TINUVIN ® 123⁵ 0.60 0.60 SilicaDispersion from above 26.4 20.0 Polysiloxane polyol from 1.00 1.00 aboveCYMEL ® 1130⁶ 29.9 29.9 RESIMENE ® 741⁷ 11.3 9.9 ¹2-Butoxyethyl acetatesolvent is commercially available from Union Carbide Corp.²2-(2-Butoxyethoxy) ethyl acetate is commercially available from UnionCarbide Corp.³2-(2H-Benzotriazol-2yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenolUV absorber available from Ciba Specialty Chemicals Corp. ⁴Stericallyhindered amine light stabilizer commercially available from CibaSpecialty Chemicals Corp.⁵Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate hinderedaminoether light stabilizer available from Ciba Specialty ChemicalsCorp. ⁶Methylated and butylated melamine-formaldehyde resin availablefrom Cytec Industries, Inc. ⁷Methylated melamine-formaldehyde resinavailable from Solutia Inc.

The pre-mixtures of ingredients from Pre-Mixes 1, 2, 3 and 4 were usedin Coating Compositions 5-16. The components for forming CoatingCompositions 5-16 are listed below in Tables 7-9. The amounts listed arethe total parts by weight in grams and the amount within parenthesis arepercentages by weight based on the weight of the resin solids of thecomponents which form the composition. Each component was mixedsequentially with agitation.

Example 28

Silylated compounds for use in the coating compositions disclosed belowwere prepared as follows:

Silylated Compound A

This example illustrates the preparation of a silylated compound that isa half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

A reaction vessel equipped with stirrer, thermocouple, temperaturecontrol, pumps and fitted with valved ports was charged with 1202.9grams trimethylolpropane (commercially available from Bayer USA), 14.4grams of triphenyl phosphine (commercially available from Aldrich®),12.1 grams of triisooctyl phosphite (commercially available from GESpecialty Chemicals), and 800.0 grams of n-butyl acetate (commerciallyavailable from Union Carbide Chemicals and Plastics Co., Inc.).

The reactor was heated to 115° C. and 4436.7 grams ofmethylhexahydrophthalic anhydride (commercially available from MillikenChemical) were added over 90 minutes, and then held 4 hours at 115° C.1533.4 grams of propylene oxide (commercially available from FisherScientific Company) was charged to the reactor over 1 hour. The reactionwas held 4 hours until the acid value was less 5.38 mg KOH/gram.Residual propylene oxide was removed by vacuum distilling at 60 to 80 mmHg at 96° C. max. The resultant product had a total solids content of95.25%.

This product was silylated by the following procedure: 637.6 grams(95.25% solids) of the previously described material were charged to areaction flask equipped with an overhead stirrer, nitrogen inlet,thermocouple, addition funnel, and condenser. The temperature wasincreased to 110° C. for one hour with nitrogen sparge to ensure thatthe system was dry. The temperature was then decreased to 85° C. undernitrogen blanket, at which time 180.9 grams hexamethyldisilazane(commercially available from Aldrich®) were added drop-wise over a 30minute period. The reaction was allowed to continue one additional hour,at which time a nitrogen sparge was introduced. The reaction wasconsidered complete when the size of the IR peak corresponding to thehydroxyl moiety was negligible. The solution was allowed to continuestirring under nitrogen sparge at 85° C. until the ammonia (by-product)was removed. Theoretical resin solids content was 96.3%.

Silylated Compound B

This example illustrates the preparation of a silylated compound that isa half-acid ester of methyl hexahydrophthalic anhydride andtrimethylolpropane with residual carboxyl groups reacted with propyleneoxide.

A reaction vessel equipped with stirrer, thermocouple, temperaturecontrol, pumps and fitted with valved ports was charged with 550.0 gramstrimethylolpropane (commercially available from Bayer USA), 6.8 grams oftriphenyl phosphine (commercially available from Aldrich®), 5.57 gramsof triisooctyl phosphite (commercially available from GE SpecialtyChemicals), and 205.7 grams of n-butyl acetate (commercially availablefrom Union Carbide Chemicals and Plastics Co., Inc.). The reaction washeated to 115° C. 2030 grams of methylhexylhydrophthalic anhydride(commercially available from Milliken Chemical) was added over 90minutes. The reaction was held 4 hours at 115° C. The reactor was cooledto 100° C. and 769.9 grams of propylene oxide (commercially availablefrom Fisher Scientific Company) was added over 1 hour. The reaction washeld 5 hours at 100° C. until the acid value was 3.1 mg KOH/gram.Residual propylene oxide was removed by vacuum distilling at 60 to 80 mmHg at 70° C. The resultant product had a total solids content of 95.08%.The product was thinned to 80.0% solids with butyl acetate.

This product was silylated by the following procedure: 3449.3 grams(80.0% solids) of the previously described material were charged to areaction

TABLE 9 COATING COMPOSITION Ingredient 14 15 16 Pre-mix 4 97.6 (64.8)97.6 (64.8) 97.6 (64.8) Pre-mix 2 — 33.6 (22.6) 16.8 (11.3) Resin B 53.8(45.2) 26.9 (22.6) 40.4 (33.9) Polybutyl acrylate¹ 0.67 (0.40) 0.67(0.40) 0.67 (0.40) Acid catalysts² 1.43 (1.00) 1.43 (1.00) 1.43 (1.00)Reduction Information: Methyl n-amyl ketone 0.62 2.7 1.48 ButylCellosolve ® acetate³ 1.25 5.4 2.95 Butyl Carbitol ® acetate⁴ 0.21 0.900.49 Spray viscosity⁵ (sec) 27 28 28 Paint temperature (° F.) 74 74 74230° F. (110° C.) % Solids⁶ 66 63 63 ¹A flow control agent having a Mwof 6700 and a Mn of 2600 made in xylene at 60% solids available fromDuPont. ²Dodecyl benzene sulfonic acid solution available fromChemcentral. ³2-Butoxyethyl acetate solvent is commercially availablefrom Union Carbide Corp. ⁴2-(2-Butoxyethoxy) ethyl acetate iscommercially available from Union Carbide Corp. ⁵Viscosity measured inseconds with a #4 FORD efflux cup at ambient temperature. ⁶% Solids of acoating is determined by taking a specific quantity of the coating andadding it into a tarred aluminum dish and recording the coating weight.Three milliliters of xylene is added into the aluminum dish to dissolveand/or disperse the coating. The coating is then heated in an oven forsixty minutes at 230° F. (110° C.). After removal from the oven, thealuminum dish is cooled, re-weighed, and the non-volatile content(weight percent solids) is # calculated using the following equation: %Solids = (F - T) ÷ (I - T) * 100. Where: F = Final weight of remainingcoating and aluminum dish in grams, I = Initial weight of coating andaluminum dish in grams, T = Tare weight of the aluminum dish in grams,and 100 is the conversion factor to percentage.

Testing

Coating Compositions 1-12 were spray applied over a pigmented basecoatto form color-plus-clear composite coatings over primed electrocoatedsteel panels. The panels used were cold rolled steel panels (size 4inches×12 inches (10.16 cm by 30.48 cm)) coated with ED5100 electrocoatand PCV70100M primer, both available from PPG Industries, Inc. The testpanels are available as APR30471 from ACT Laboratories, Inc. ofHillsdale, Mich.

Coating Compositions 1-5 were tested over two different basecoats,namely: HWB9517, a black pigmented water-based acrylic/melamine basecoatcommercially available from PPG Industries, Inc, and a black pigmentedwater-based acrylic/melamine basecoat (Basecoat X), the formulation forwhich is given below. Coating Compositions 6-12 were evaluated overBasecoat X.

Basecoat X Parts by weight Ingredient (grams) Solid weights (grams)Hexyl Cellosolve ®¹ 20.0 — 2-Butoxyethanol 20.0 — Phosphatized Epoxy²1.00 0.60 TINUVIN 1130³ 3.00 3.00 CYMEL 1156⁴ 25.0 25.0 VISCOLAM 330⁵3.33 1.00 Deionized Water 100.0 — Odorless Mineral Spirits⁶ 20.0 —BYK-032⁷ 3.90 2.00 Acrylic Latex⁸ 125.3 51.5 SETALUX 6802 AQ-24⁹ 61.215.0 Amine¹⁰ 3.00 — Black tint paste¹¹ 47.6 11.5 ¹Ethylene glycolmonohexyl ether solvent commercially available from Union Carbide Corp.²Phosphatized epoxy prepared from EPON 828, a polyglycidyl ether ofBisphenol A available from Shell Oil and Chemical Co.; reacted withphosphoric acid in an 83:17 weight ratio. ³Substituted hydroxyphenylbenzotriazole available from Ciba Specialty Chemicals Corp. ⁴Methylatedmelamine formaldehyde resin available from Cytec Industries, Inc.⁵Acrylic thickener available from Lamberti in Italy. ⁶Solvent availablefrom Shell Chemical Co. ⁷Defoamer available from Byk Chemie. ⁸TheAcrylic Latex was prepared as follows: The polyester was prepared in afour-neck round bottom flask equipped with a thermometer, mechanicalstirrer, condenser, dry nitrogen sparge, and a heating mantle. Thefollowing ingredients were used: 1103.0 g isostearic acid 800.0 gpentaerythritol 470.0 g crotonic acid 688.0 g phthalic anhydride 6.1 gdibutyltin oxide 6.1 g triphenyl phosphite 1170.0 g butyl acrylate 4.0 gIonol (butylated hydroxytoluene) The first six ingredients were stirredin the flask at 210° C. until 245 ml of distillate was collected and theacid value dropped to 46. The material was cooled to 77° C. and the lasttwo ingredients were stirred in. The final product was a viscous yellowliquid with a hydroxyl value of 54.0, a Gardner-Holdt viscosity of Z+, aweight average molecular weight of 45,600, and a non-volatile content of70.2%. A pre-emulsion was prepared by stirring together the followingingredients: 286.0 g polyester of example III 664.0 g butyl acrylate30.0 g ethylene glycol dimethacrylate 20.0 g acrylic acid 46.4 gdodecylbenzenesulfonic acid (70% in isopropanol) 14.3 gdimethylethanolamine 1000.0 g water The reaction was carried out usingthe same procedure and materials as in Latex Example I. The reactionexothermed from 23° C. to 80° C. The final pH of the latex was 6.1, thenonvolatile content was 42.4% the particle size was 105 nm, and theBrookfield viscosity was 14 cps (spindle #1, 50 rpm). ⁹Rheology controlagent available from Akzo Nobel. ¹⁰Dimethylethanolamine, 50% Aqueous,available from Union Carbide Corp. ¹¹Black pigment available from CabotCorp. as MONARCH BLACK 1300 dispersed in an acrylic grind vehicle (35%butyl acrylate, 30% styrene, 18% butyl methacrylate, 8.5% 2-hydroethylacrylate, 8.5% acrylic acid) at a total pigment to binder ration (P/B)of 0.35.

Two coats of basecoat were automated spray applied to the electrocoatedand primed steel panels at ambient temperature (70° F. (21° C.)). Noflash was permitted between the application of the two basecoat layers.The total dry film thickness of the basecoat ranged from 0.5 to 0.7 mils(13 to 17 micrometers) was targeted. After the second basecoatapplication, a 1 to 10 minute air flash at ambient temperature was givenbefore force flashing the basecoated panels. For panels basecoated withHWB9517, the force flash was ten minutes at 200° F. (93° C.). The panelsbasecoated with Basecoat X were forced flashed for five minutes at 200°F. (93° C.). Coating Compositions 1-12 were each automated spray appliedto a basecoated panel at ambient temperature in two coats with a ninetysecond ambient flash between applications. Total clearcoat was appliedat a 1.6 to 1.8 mils (41 to 46 micrometers) dry film thickness. Allcoatings were allowed to air flash at ambient temperature for tenminutes. Panels prepared from each coating were baked for thirty minutesat 285° F. (141° C.) to fully cure the coating(s). The panels were bakedin a horizontal position.

To test recoat adhesion, each panel was coated with another layer ofbasecoat and clearcoat or clearcoat only, as specified below. Examples1-5 were recoated with HWB9517 or Basecoat X and Coating Compositions1-5, depending on the respective original panel. Examples 6-12 wererecoated with Basecoat X and Coating Compositions 6-12, depending on therespective original panel. For example, Coating Composition 5 overHWB9517 original (prepared above) was recoated with HWB9517 and CoatingComposition 5 clearcoat. Half of an original panel from Examples 1-12was basecoated and clearcoated and the other half of the panel wasclearcoated only. To recoat the panels, the bottom halves of theoriginal panels were covered with aluminum foil and then the respectivebasecoats were automated spray applied as described above. The foil wasremoved, resulting in an original panel with the upper half coated inbasecoat and the bottom half still with only the original coatinglayers. The panels were force flashed as described above. The respectiveclearcoat was then automated spray applied to the entire panel asdescribed above. The resulting panels were half coated inbasecoat/clearcoat from the original spray application and another layerof basecoat/clearcoat from the recoat spray application (B/C//B/C). Theother half of the resulting panel was coated in basecoat/clearcoat fromthe original spray application and another layer of clearcoat from therecoat spray application (B/C//C).

Properties for the coatings are reported below in Table 10 for Examples1-5 over HWB9517 basecoat and Table 11 for Examples 1-12 over BasecoatX.

TABLE 10 % 20° Gloss Retained after scratch testing² Initial Postweathering³ Knoop Recoat Adhesion⁵ Example # 20° Gloss¹ Initial 286Hours 618 Hours Hardness⁴ B/C//B/C B/C//C 1 85 79 82 84 10.3 0 0 2 85 1825 58 4.0 0 0 3 84 1 5 8 <2.0 0  4+ 4 84 6 14 20 <2.0 0 4 5 83 1 13 18<2.0 0 4

TABLE 11 % 20° Gloss Retained after scratch testing² Initial Postweathering³ Knoop Recoat Adhesions⁵ Example # 20° Gloss¹ Initial 286Hours 618 Hours Hardness⁴ B/C//B/C B/C//C 1 87 91 84 71 12.7 0 0 2 87 7880 64 9.9  4+ 0 3 87 27 20 20 13.8 5  4+ 4 88 81 28 26 11.5  4+ 4 5 8871 53 44 9.9  4+ 4 6 87 91 — — 10.9 1 0 7 86 67 — — 7.7  4+ 0 8 87 67 —— 8.1  4+ 0 9 85 91 — — 10.4 4 0 10 87 49 — — 5.8  4+  4+ 11 85 67 — —6.7 4  1+ 12 87 59 — — 6.6  4+  3+ ¹20° gloss was measured with aStatistical Novo-Gloss 20° gloss meter, available from Paul N. GardnerCompany, Inc. ²Coated panels were subjected to scratch testing bylinearly scratching the coated surface with a weighted abrasive paperfor ten double rubs using an Atlas AATCC Scratch Tester, Model CM-5,available from Atlas Electrical Devices Company of Chicago, Illinois.The abrasive paper used was 3M 281Q WETORDRY ™ PRODUCTION ™ 9 micronpolishing paper sheets, which are commercially available from 3M Companyof St. Paul, Minnesota. Panels were then # rinsed with tap water andcarefully patted dry with a paper towel. The 20° gloss was measured(using the same gloss meter as that used for the initial 20° gloss) onthe scratched area of each test panel. Using the lowest 20° glossreading from the scratched area, the scratch results are reported as thepercent of the initial gloss retained after scratch testing using thefollowing calculation: 100% * scratched gloss ÷ initial gloss. Highervalues # for percent of gloss retained are desirable. ³Post-weatheringscratch resistance (retained scratch resistance) was measured using thescratch test method described above after the unscratched test panelswere subjected to simulated weathering by exposure to UVA-340 bulbs in aQUV Accelerated Weathering Tester available through Q Panel LabProducts. Testing was as follows: a cycle of 70° C. for 8 hours exposureto UVA followed by a condensation cycle at 50° C. for 4 hours with noUVA (total test # time is reported in the table). Using the lowest 20°gloss reading from the scratched area, the scratch results are reportedas the percent of the initial gloss retained after post-weatheringscratch testing using the following calculation: 100% * post-weatheringscratched gloss ÷ initial gloss. Higher values for percent of glossretained are desirable. ⁴Knoop hardness is a hardness measurementderived from the size of an indentation in the coating made using theTukon Microhardness Instrument. The Tukon Microhardness Instrument makesan indentation in a cured coating by applying a 25 gram load to thesurface with a diamond tip. The size of the indentation is measuredusing a microscope. That indentation size is then converted to the KnoopHardness measurement. The # Tukon Microhardness Instrument used was theTukon Microhardness Tester Model 300 manufactured by Wilson Instruments,Division of Instron Corporation. ⁵Recoat adhesion tests the adhesion ofthe recoat layer (either basecoat/clearcoat or clearcoat only) to theoriginal layers (steel/electrodeposition/primer/basecoat/clearcoat) tosimulate repair coatings. An eleven-blade claw with 1.5 mm spaced teeth(blade and handle/blade holder are available from Paul N. GardnerCompany, Inc.) was used to scribe the cured coating. Two sets of scribeswere made by scribing the second set on top of and perpendicular to thefirst set. Detached flakes and ribbons of coating were wiped off thepanel and strapping tape (3M #898 available from 3M Company) wassmoothed firmly over the crosshatch marking. Within 90 seconds ofapplication, the tape was removed in one continuous motion directedtoward the tester and as parallel to the panel as possible. The scribedarea was inspected # and rated for removal of the recoat layer to thesubstrate according to the following scale: 5 = The edges of the cutsare completely smooth and none of the lattice squares is detached. 4 =Small flakes of coating are detached at intersections. Less than fivepercent of the area is affected. 3 = Small flakes of the coating aredetached along edges and at intersections of cuts. The area affected isfive to fifteen percent of the lattice. 2 = The coating has flaked alongthe edges and on parts of the squares. The area affected is fifteen tothirty-five percent of the lattice. 1 = The coating has flaked along theedges of cuts in large ribbons and whole squares have detached. The areaaffected is thirty-five to sixty-five percent of the lattice. 0 =Flaking and detachment worse than rating 1. Over sixty-five percent ofthe lattice is affected.

Example 29

A dual cure (ultraviolet radiation and thermal cure) coating compositionwas prepared and evaluated as discussed below.

The coating composition was made by adding each of the ingredients underagitation in the order listed in the table below. The acrylic polyol andisocyanurate were preblended before the addition to the otheringredients.

Ingredient Description Solids Weight SR355¹ DiTMP Tetraacrylate 27.327.3 Clariant HIGHLINK OG Colloidal Silica in 41.9 41.9 108-32tripropylene glycol diacrylate DAROCURE 4265³ Photoinitiator 2.0 2.0TINUVIN 400³ UV Absorber 3.0 3.0 TINUVIN 292³ Hindered Amine Light 0.80.8 Stabilizer RC-68-1497² Acrylic Polyol Resin 15.6 23.3 DESMODURN-3300⁴ Isocyanurate of HDI 9.4 9.4 Total 100.0 107.7¹Ditrimethylolpropane tetraacrylate which is available from SartomerCompany, Inc. ²BMA (14.5), BA (14.5), HEMA (20.4), HPMA (22.6) IsobornylMA (27.6), AA (0.4). Acrylic polyol comprising 14.5% BA, 14.5% BMA,27.6% IBoMA, 22.6% HPMA, 20.4% HEMA, 0.4% AA, and exhibiting thefollowing properties: solids 67% in AROMATIC 100 available from Exxon,Mw 2336, Mn 1236, OH value 116.8. ³Available from Ciba-GeigyCorporation. ⁴Available from Bayer Corporation.

The coating composition was applied over pretreated and basecoatedpanels as described below. The panels used were cold rolled steel panels(size 4 inches×12 inches (10.16 cm by 30.48 cm)) coated with ED5000electrocoat (available from PPG Industries, Inc). The test panels areavailable from ACT Laboratories, Inc. of Hillsdale, Mich. The basecoat(BWB-8555 black waterborne basecoat available from PPG Industries, Inc.)was spray applied at 0.6 mils (15 micrometers) dry film thickness andfully baked for 30 minutes at 285° F. (141° C.). The coating compositionof the present invention was applied using a 7 mil (179 micrometers)drawdown bar over the basecoat to approximately 1.0-1.2 mils (26-31micrometers) dry film thickness. The clearcoat was flashed at ambienttemperature (25° C.) for five minutes and then cured using ultravioletlight at 576 mJoules/cm² at a line speed of 70 feet per minute (21.3meters per minute) and then thermally cured for 30 minutes at 285° F.(141° C.).

The coating on the panel was evaluated for scratch resistance asfollows. 20° gloss was measured with a Statistical Novo-Gloss 20° glossmeter, available from Paul N. Gardner Company, Inc. Coated panels weresubjected to scratch testing by linearly scratching the coated surfacewith a weighted abrasive paper for ten double rubs using an Atlas AATCCScratch Tester, Model CM-5, available from Atlas Electrical DevicesCompany of Chicago, Ill. The abrasive paper used was 3M 281Q WETORDRY™PRODUCTION™ 9 micron polishing paper sheets, which are commerciallyavailable from 3M Company of St. Paul, Minn. Panels were then rinsedwith tap water and carefully patted dry with a paper towel. The 20°gloss was measured (using the same gloss meter as that used for theinitial 20° gloss) on the scratched area of each test panel. Using thelowest 20° gloss reading from the scratched area, the scratch resultsare reported as the percent of the initial gloss retained after scratchtesting using the following calculation: 100%* scratched gloss÷initialgloss. Higher values for percent of gloss retained are desirable.

The test results are given in Table 12 below.

TABLE 12 Initial 20° 20° Gloss after Scratch % Gloss Clearcoat GlossTesting Retention UV/Thermal Dual 82 79 96 Cure

Example 30

A polysiloxane polyol was prepared that was a product of thehydrosilylation of a reactive silicone fluid with an approximate degreeof polymerization of 3 to 7, i.e., (Si—O)₃ to (Si—O)₇. The polysiloxanepolyol was prepared from a proportionately scaled-up batch of thefollowing mixture of ingredients in the ratios indicated:

Equivalent Parts By Weight Ingredients Weight Equivalents (kilograms)Charge I: Trimethylolpropane 174.0 756.0 131.54 monoallyl ether ChargeII: MASILWAX BASE¹ 156.7² 594.8 93.21 Charge III: Chloroplatinic acid 10ppm Toluene 0.23 Isopropanol 0.07 ¹Polysiloxane-containing siliconhydride, commercially available from BASF Corporation. ²Equivalentweight based on mercuric bichloride determination.

To a suitable reaction vessel equipped with a means for maintaining anitrogen blanket, Charge I and an amount of sodium bicarbonateequivalent to 20 to 25 ppm of total monomer solids was added at ambientconditions and the temperature was gradually increased to 75° C. under anitrogen blanket. At that temperature, 5.0% of Charge II was added underagitation, followed by the addition of Charge III, equivalent to 10 ppmof active platinum based on total monomer solids. The reaction was thenallowed to exotherm to 95° C. at which time the remainder of Charge IIwas added at a rate such that the temperature did not exceed 95° C.After completion of this addition, the reaction temperature wasmaintained at 95° C. and monitored by infrared spectroscopy fordisappearance of the silicon hydride absorption band (Si—H, 2150 cm⁻¹).

Silica Dispersion AA

A colloidal silica dispersion was prepared as follows. A 4-neck reactionflask equipped for vacuum distillation was flushed with N₂. To thereaction flask was added 1500.9 g of the polysiloxane polyol describedabove, 3751.1 of ORGANOSILICASOL™ MT-ST colloidal silica which iscommercially available from Nissan Chemicals and 960.4 g of methyl amylketone. The resulting mixture was vacuum distilled at 70 mm Hg and 31°C.

Film Forming Compositions

Formulation pre-mixtures: (each component was mixed sequentially withagitation)

Example 1 (99-346-91A)

Parts by weight Ingredient (grams) Solid weights (grams) Methyl n-amylketone 18.0 — Butyl Cellosolve ® acetate¹ 18.0 — Butyl Carbitol ®acetate² 4.0 — TINUVIN ® 928³ 3.0 3.0 TINUVIN ® 292⁴ 0.40 0.40¹2-Butoxyethyl acetate solvent is commercially available from UnionCarbide Corp. ²2-(2-Butoxyethoxy) ethyl acetate is commerciallyavailable from Union Carbide Corp.³2-(2H-Benzotriazol-2yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenolUV absorber available from Ciba Specialty Chemicals Corp. ⁴Stericallyhindered amine light stabilizer commercially available from CibaSpecialty Chemicals Corp.

The pre-mixture of ingredients from Example 1 was used in Examples 2 and3. Compositions for Examples 2 and 3 are listed below in Table 1. Theamounts listed are the total parts by weight in grams and the amountwithin parenthesis are percentages by weight based on weight of resinsolids. Each component was mixed sequentially with agitation.

TABLE 13 Example 2 Example 3 Ingredient (99-346-93A) (99-346-93B)Example 1 Pre-mix 43.4 (3.4) 43.4 (3.4) Silica Dispersion AA 10.0 (7.0)10.0 (7.0) RESIMENE 757¹ 11.8 (11.4) 11.8 (11.4) Acrylic² 100.8 (65.5)74.9 (48.7) Polybutyl acrylate³ 0.50 (0.30) 0.50 (0.30) Blocked acidcatalyst⁴ 2.50 (1.00) 2.50 (1.00) CYLINK ® 2000⁵ 37.1 (19.1) — TRIXENEDP9B/1494⁶ — 51.3 (35.9) Reduction Information: Methyl n-amyl ketone2.39 — Butyl Cellosolve ® acetate⁷ 2.39 — Butyl Carbitol ® acetate⁸ 0.53— Spray viscosity⁹ (sec) 29 26 Paint temperature (° F.) 73 74¹Methylated and butylated melamine-formaldehyde resin available fromSolutia Inc. ²Acrylic resin (30% styrene, 19.9% hydroxyethylmethacrylate, 28.7% CarduraE (available from Shell Chemical Co.), 9.5%acrylic acid, and 12% ethylhexyl acrylate) at 65% solids in SOLVESSO 100(available from Exxon Chemicals America). ³A flow control agent having aMw of 6700 and a Mn of 2600 made in xylene at 60% solids available fromDuPont. ⁴Dodecyl benzene sulfonic acid solution, blocked withdiisopropanol amine to 91% total neutralization, 40% acid solids inethanol. ⁴Dodecyl benzene sulfonic acid solution available fromChemcentral. ⁵Tris(alkylcabamoyl)triazine crosslinker available fromCYTEC Industries, Inc. ⁶3,5-Dimethylpyrazole blocked isocyanurate ofisophorone diisocyanate available from Baxenden Chemicals Limited.⁷2-Butoxyethyl acetate solvent is commercially available from UnionCarbide Corp. ⁸2-(2-Butoxyethoxy) ethyl acetate is commerciallyavailable from Union Carbide Corp. ⁹Viscosity measured in seconds with a#4 FORD efflux cup at ambient temperature.

Testing

The film forming compositions of Examples 2 and 3 were spray applied toa pigmented basecoat to form color-plus-clear composite coatings overprimed electrocoated steel panels. The panels used were cold rolledsteel panels (size 4 inches×12 inches (10.16 cm by 30.48 cm)) coatedwith ED5100 electrocoat and PCV70100M primer, both available from PPGIndustries, Inc. The test panels are available as APR30471 from ACTLaboratories, Inc. of Hillsdale, Mich.

A black pigmented water-based acrylic/melamine basecoat, available fromPPG Industries, Inc. (Basecoat Z) was used. The formulation for BasecoatZ is given below.

Basecoat Z Parts by weight Ingredient (grams) Solid weights (grams)n-butoxypropanol, PNB¹ 45.0 — CYMEL 327² 38.9 35.0 TINUVIN 1130³ 3.203.20 Phosphotized Epoxy⁴ 0.80 0.50 Amine⁵ 2.00 — Acrylic Latex⁶ 109.446.5 Odorless Mineral Spirits⁷ 8 — Polyurethane acrylic⁸ 42.6 10.0 Blacktint paste⁹ 47.6 11.5 Amine⁵ 1.00 — DeIonized Water 67.7 — ¹Solventavailable from Lyondell Petrochemical. ²Methylated melamine formaldehyderesin available from Cytec Industries, Inc. ³Substituted hydroxyphenylbenzotriazole available from Ciba Specialty Chemicals Corp.⁴Phosphatized epoxy prepared from Epon 828, a polyglycidyl ether ofBisphenol A available from Shell Oil and Chemical Co.; # reacted withphosphoric acid in an 83:17 weight ratio. ⁵Dimethylethanolamine, 50%aqueous, available from Union Carbide Corp. ⁶The Acrylic Latex wasprepared as follows: The polyester was prepared in a four-neck roundbottom flask equipped with a thermometer, mechanical stirrer, condenser,dry nitrogen sparge, and a heating mantle. The following ingredientswere used: 1103.0 g isostearic acid 800.0 g pentaerythritol 470.0 gcrotonic acid 688.0 g phthalic anhydride 6.1 g dibutyltin oxide 6.1 gtriphenyl phosphite 1170.0 g butyl acrylate 4.0 g Ionol (butylatedhydroxytoluene) The first six ingredients were stirred in the flask at210° C. until 245 ml of distillate was collected and the acid valuedropped to 46. The material was cooled to 77° C. and the last twoingredients were stirred in. The final product was a viscous yellowliquid with a hydroxyl value of 54.0, a Gardner-Holdt viscosity of Z+, aweight average molecular weight of 45,600, and a non-volatile content of70.2%. A pre-emulsion was prepared by stirring together the followingingredients: 286.0 g polyester of example III 664.0 g butyl acrylate30.0 g ethylene glycol dimethacrylate 20.0 g acrylic acid 46.4 gdodecylbenzenesulfonic acid (70% in isopropanol) 14.3 gdimethylethanolamine 1000.0 g water The reaction was carried out usingthe same procedure and materials as in Latex Example I. The reactionexothermed from 23° C. to 80° C. The final pH of the latex was 6.1, thenonvolatile content was 42.4%, the particle size was 105 nm, and theBrookfield viscosity was 14 cps (spindle #1, 50 rpm). ⁷Solvent availablefrom Shell Chemical Co. ⁸Polyurethane acrylic composed of 4% dimethylolpropionic acid, 16% Desmodur W (available from Bayer), 9.3% dimeryldiisocyanate, 22.8% FORMREZ 66-56 (Witco Corp), 5.7% MPEG 2000 (UnionCarbide Corp.), 22.6% methyl methacrylate, 15.6% butyl acrylate, 1.6%ethyleneglycol dimethacrylate, 2.1% diethylene triamine, 0.3% ammoniumpersulfate. ⁹Black pigment available from Cabot Corp. as MONARCH BLACK1300 dispersed in an acrylic grind vehicle (35% butyl acrylate, 30%styrene, 18% butyl methacrylate, 8.5% 2-hydroxyethyl acrylate, 8.5%acrylic acid) at a total pigment to binder ratio (P/B) of 0.35.

The basecoats was automated spray applied in two coats to theelectrocoated and primed steel panels at ambient temperature (70° F.(21° C.)). No flash was given between the two basecoat applications. Atotal dry film thickness of 0.66 mils (17 micrometers) was targeted.After the second basecoat application, a 1 to 10 minute air flash atambient temperature was given before force flashing the basecoatedpanels. The force flash was five minutes at 200° F. (93° C.). The clearcoating compositions of Examples 2 and 3 were each automated sprayapplied to the basecoated panel at ambient temperature in two coats witha ninety second ambient flash between applications. Total dry filmthickness for the clearcoats was 1.78 mils (45 micrometers). Allcoatings were allowed to air flash at ambient temperature for tenminutes. Panels prepared from each coating were baked for thirty minutesat 285° F. (141° C.) to fully cure the coating(s). The panels were bakedin a horizontal position.

Properties for the coatings are reported below in Table 14.

TABLE 14 % 20° Gloss Retained after scratch testing² Initial Postweathering³ Example # 20° Gloss¹ Initial 240 Hours 504 Hours 1028 Hours2 92 92 84 51 32 3 90 79 85 49 29 ¹20° gloss was measured with aStatistical Novo-Gloss 20° gloss meter, available from Paul N. GardnerCompany, Inc. ²Coated panels were subjected to scratch testing bylinearly scratching the coated surface with a weighted abrasive paperfor ten double rubs using an Atlas AATCC Scratch Tester, Model CM-5,available from Atlas Electrical Devices Company of Chicago, Illinois.The abrasive paper used was 3M 281Q WETORDRY ™ PRODUCTION ™ 9 micronpolishing paper sheets, which are commercially available from 3M Companyof St. Paul, Minnesota. Panels were then rinsed with # tap water andcarefully patted dry with a paper towel. The 20° gloss was measured(using the same gloss meter as that used for the initial 20° gloss) onthe scratched area of each test panel. Using the lowest 20° glossreading from the scratched area, the scratch results are reported as thepercent of the initial gloss retained after scratch testing using thefollowing calculation: 100% * scratched gloss ÷ initial gloss. Highervalues for percent of gloss # retained are desirable. ³Post-weatheringscratch resistance (retained scratch resistance) was measured using thescratch test method described above after the unscratched test panelswere subjected to simulated weathering by exposure to UVA-340 bulbs in aQUV Accelerated Weathering Tester available through Q Panel LabProducts. Testing was as follows: a cycle of 70° C. for 8 hours exposureto UVA followed by a # condensation cycle at 50° C. for 4 hours with noUVA (total test time is reported in the table). Using the lowest 20°gloss reading from the scratched area, the scratch results are reportedas the percent of the initial gloss retained after post-weatheringscratch testing using the following calculation: 100% * post-weatheringscratched gloss ÷ initial gloss. Higher values for percent of glossretained are desirable.

Example 31

A coating composition of the present invention was prepared from amixture of the following ingredients:

Resin Total Weight Ingredients Solids (%) (Grams Butyl Acetate — 11.1DOWANOL PM Acetate — 28.6 Butyl Cellusolve Acetate — 4.1 Tinuvin 928 3.03.0 Silica dispersion of Example 23C 6.7 8.8 Polysiloxane polyol ofExample A 10.3 10.3 Cymel 202 15.0 18.8 Acrylic polyol¹ 22.5 31.5Setalux C-71761 VB-60² 20.4 34.9 Tinuvin 292 0.5 0.5 Catalyst of Example12 0.5 0.67 DESMODUR N3300 23.4 23.4 DESMODUR Z4470 3.5 5.0 ¹Acrylicpolyol comprising 14.5% BA, 14.5% BMA, 27.6% IBoMA, 22.6% HPMA, 20.4%HEMA, 0.4% AA, Mn 1700, Mw 3227. ²Thermosetting hydroxylated acryliccopolymer containing sag control agent available from AKZO Nobel

A coating composition of the present invention was also prepared from amixture of the following ingredients:

Resin Total Weight Ingredients Solids (%) (Grams Ethyl3-ethoxypropionate — 38.7 Tinuvin 928 3.0 3.0 Silica dispersion ofExample 23C 6.7 8.8 Polysiloxane polyol of Example A 10.3 10.3 Cymel 2027.5 9.4 Acrylic polyol¹ 39.0 57.9 Tinuvin 292 1.0 1.0 Catalyst ofExample 12 0.5 0.7 DESMODUR N3300 16.6 16.6 DESMODUR Z4470 21.9 31.3¹Acrylic polyol comprising 19% BA, 18.5% BMA, 40% HPA, 20% Styrene, 0.5%MMA, 2% AA Mw 7100

The compositions of the present invention can provide numerousadvantages in coating applications, including, but not limited to, goodinitial and retained mar resistance, good appearance properties such asgloss and distinctiveness of image, and physical properties such as goodflexibility and weatherability.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications which are within the spirit and scopeof the invention, as defined by the appended claims.

Therefore, we claim:
 1. A cured coating formed from a composition formedfrom components comprising: (a) at least one polysiloxane comprising atleast one reactive functional group, the at least one polysiloxanecomprising at least one of the following structural units (I): ImagePage 2 R¹ _(n)R² _(m)SiO_((4−n−m)/2)  (I)  wherein each R¹, which may beidentical or different, represents H, OH, a monovalent hydrocarbongroup, or a monovalent siloxane group; each R², which may be identicalor different, represents a group comprising at least one functionalgroup, wherein m and n fulfill the requirements of 0<n<4, 0<m<4 and2<(m+n)<4; and (b) at least one reactant comprising at least onefunctional group that is reactive with at least one functional groupselected from the at least one reactive functional group of the at leastone polysiloxane and at least one functional group of the at least onereactant; and (c) a plurality of particles selected from inorganicparticles, composite particles, and mixtures thereof; wherein eachcomponent is different, wherein a retained scratch resistance value ofthe cured coating is greater than a retained scratch resistance value ofa cured coating that does not contain the plurality of particles whereineach component is different, and wherein the cured coating has aninitial scratch resistance value such that after scratch testing greaterthan 40 percent of the initial 20° gloss is retained.
 2. A cured coatingcomposition according to claim 1, wherein each R², which may beidentical or different, represents a group comprising at least onereactive functional group selected from a hydroxyl group, a carboxylgroup, an isocyanate group, a blocked polyisocyanate group, a primaryamine group, a secondary amine group, an amide group, a carbamate group,a urea group, a urethane group, a vinyl group, an unsaturated estergroup, a maleimide group, a fumarate group, an anhydride group, ahydroxy alkylamide group, and an epoxy group.
 3. A cured coatingaccording to claim 1, wherein the at least one polysiloxane comprises atleast two reactive functional groups.
 4. A cured coating according toclaim 1, wherein at least one group represents a group comprising atleast one reactive functional group selected from a hydroxyl group and acarbamate group.
 5. A cured coating according to claim 4, wherein atleast one R² group represents a group comprising at least two reactivefunctional groups selected from a hydroxyl group and a carbamate group.6. A cured coating according to claim 1, wherein at least one R² grouprepresents a group comprising an oxyalkylene group and at least twohydroxyl groups.
 7. A cured coating according to claim 1, wherein the atleast one polysiloxane, when added to the other components of thecomposition, is present in the composition in an amount ranging from0.01 to 90 weight percent based on total weight of the resin solids ofthe components which form the composition.
 8. A cured coating accordingto claim 7, wherein the at least one polysiloxane is present in anamount of at least 2 weight percent.
 9. A cured coating according toclaim 8, wherein the at least one polysiloxane is present in an amountof at least 5 weight percent.
 10. A cured coating according to claim 9,wherein the at least one polysiloxane is present in an amount of atleast 10 weight percent.
 11. A cured coating according to claim 1,wherein the particles are selected from fumed silica, amorphous silica,colloidal silica, alumina, colloidal alumina, titanium oxide, cesiumoxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia andmixtures of any of the foregoing.
 12. A cured coating according to claim1, wherein the particles are surface treated.
 13. A cured coatingaccording to claim 1, wherein the particles include colloidal silica.14. A cured coating according to claim 1, wherein the particles have anaverage particle size less than 100 microns prior to incorporation intothe composition.
 15. A cured coating according to claim 1, wherein theparticles have an average particle size less than 50 microns prior toincorporation into the composition.
 16. A cured coating according toclaim 1, wherein the particles have an average particle size rangingfrom 1 to less than 1000 nanometers prior to incorporation into thecomposition.
 17. A cured coating according to claim 16, wherein theparticles have an average particle size ranging from 1 to 100 nanometersprior to incorporation into the composition.
 18. A cured coatingaccording to claim 17, wherein the particles have an average particlesize ranging from 5 to 50 nanometers prior to incorporation into thecomposition.
 19. A cured coating according to claim 1, wherein theparticles, when added to the other components that form the composition,are present in the composition in an amount ranging from 0.01 to 75weight percent based on total weight of the resin solids of thecomponents which form the composition.
 20. A cured coating according toclaim 19, wherein the particles are present in an amount of at least 0.1weight percent.
 21. A cured coating according to claim 19, wherein theparticles are present in an amount of at least 0.5 weight percent.
 22. Acured coating according to claim 19, wherein the particles are presentin an amount of less than 20 weight percent.
 23. A cured coatingaccording to claim 19, wherein the particles are present in an amount ofless than 10 weight percent.
 24. A cured coating according to claim 1,wherein the at least one reactant is selected from at least one curingagent.
 25. A cured coating according to claim 24, wherein the at leastone curing agent is selected from an aminoplast resin, a polyisocyanate,a blocked polyisocyanate, a polyepoxide, a polyacid, and a polyol.
 26. Acured coating according to claim 24, wherein the at least one curingagent is selected from an aminoplast resin, and a polyisocyanate.
 27. Acured coating according to claim 24, wherein the curing agent, whenadded to the other components that form the composition, is present inan amount ranging from 1 weight percent to 65 weight percent based ontotal weight of the resin solids of the components which form thecomposition.
 28. A cured coating according to claim 27, wherein thecuring agent is present in an amount of at least 5 weight percent.
 29. Acured coating according to claim 28, wherein the curing agent is presentin an amount of at least 10 weight percent.
 30. A cured coatingaccording to claim 1, wherein the components which form the compositioncomprise at least one film-forming material different from the at leastone polysiloxane (a).
 31. A cured coating according to claim 30, whereinthe at least one film-forming material is selected from at least oneadditional polymer, in addition to and different from said at least onepolysiloxane, comprising at least one reactive functional group.
 32. Acured coating according to claim 31, wherein the at least one additionalpolymer has at least one reactive functional group selected from ahydroxyl group, a carboxyl group, an isocyanate group, a blockedpolyisocyanate group, a primary amine group, a secondary amine group, anamide group, a carbamate group, a urea group, a urethane group, a vinylgroup, an unsaturated ester group, a maleimide group, a fumarate group,an anhydride group, a hydroxy alkylamide group, and an epoxy group. 33.A cured coating according to claim 32, wherein the additional polymerhas at least one reactive functional group selected from a hydroxylgroup, and a carbamate group.
 34. A cured coating according to claim 1,wherein the components which form the composition comprise at least onecatalyst.
 35. A cured coating according to claim 34, wherein the atleast one catalyst is, when added to the other components that form thecomposition, present in an amount sufficient to accelerate the reactionbetween the at least one functional group of the at least one reactantand at least one functional group selected from the at least onereactive functional group of the at least one polysiloxane and at leastone functional group of the at least one reactant.
 36. A cured coatingaccording to claim 34, wherein the at least one catalyst is an acidcatalyst.
 37. A cured coating according to claim 36, wherein the atleast one catalyst is selected from an acid phosphate, a substitutedsulfonic acid and an unsubstituted sulfonic acid.
 38. A cured coatingaccording to claim 34, wherein the at least one catalyst is phenyl acidphosphate.
 39. A cured coating according to claim 1, wherein thecomponents which form the composition comprise at least one surfaceactive agent.
 40. A cured coating according to claim 39, wherein the atleast one surface active agent is selected from an anionic surfaceactive agent, a nonionic surface active agent and a cationic surfaceactive agent.
 41. A cured coating according to claim 1, wherein the atleast one polysiloxane has the following structure (II) or (III):

wherein: m has a value of at least 1; m′ ranges from 0 to 75; n rangesfrom 0 to 75; n′ ranges from 0 to 75; each R, which may be identical ordifferent, is selected from H, OH, monovalent hydrocarbon groups,monovalent siloxane groups, and mixtures of any of the foregoing; and—R^(a) comprises the following structure (IV): —R³—X wherein —R³ isselected from an alkylene group, an oxyalkylene group, an alkylene arylgroup, an alkenylene group, an oxyalkenylene group, and an alkenylenearyl group; and X represents a group which comprises at least onereactive functional group selected from a hydroxyl group, a carboxylgroup, an isocyanate group, a blocked polyisocyanate group, a primaryamine group, a secondary amine group, an amide group, a carbamate group,a urea group, a urethane group, a vinyl group, an unsaturated estergroup, a maleimide group, a fumarate group, an anhydride group, ahydroxy alkylamide group, and an epoxy group.
 42. A cured coatingaccording to claim 41, wherein (n+m) ranges from 2 to
 9. 43. A curedcoating according to claim 41, wherein (n′+m′) ranges from 2 to
 9. 44. Acured coating according to claim 42, wherein (n+m) ranges from 2 to 3.45. A cured coating according to claim 43, wherein (n′+m′) ranges from 2to
 3. 46. A cured coating according to claim 41, wherein X represents agroup comprising at least one reactive functional group selected from ahydroxyl group and a carbamate group.
 47. A cured coating according toclaim 41, wherein X represents a group comprising at least two hydroxylgroups.
 48. A cured coating according to claim 41, wherein X representsa group comprising at least one substituent selected from H, amonohydroxy-substituted group and a group having the following structure(V): R⁴—(CH₂—OH)_(p)  (V) wherein R⁴ is

′when p is 2 and R³ is C₁ to C₄ alkyl, or R⁴ is

 when p is 3, wherein a portion of X is a group having the structure(V).
 49. A cured coating according to claim 48, wherein m is 2 and p is2.
 50. A cured coating according to claim 1, wherein the polysiloxane(a) is the reaction product of at least the following reactants: (i) atleast one polysiloxane of the formula (VI):

 wherein each substituent group R, which may be identical or different,represents a group selected from H, OH, a monovalent hydrocarbon group,a siloxane group, and mixtures of any of the foregoing; at least one ofthe groups represented by R is H, and n′ ranges from 0 to 100, such thatthe percent of Si—H content in the at least one polysiloxane of formula(VI) ranges from 2 to 50; and (ii) at least one molecule which comprisesat least one functional group selected from a hydroxyl group, a carboxylgroup, an isocyanate group, a blocked polyisocyanate group, a primaryamine group, a secondary amine group, an amide group, a carbamate group,a urea group, a urethane group, a vinyl group, an unsaturated estergroup, a maleimide group, a fumarate group, an anhydride group, ahydroxy alkylamide group, and an epoxy group and at least oneunsaturated bond capable of undergoing a hydrosilylation reaction.
 51. Acured coating according to claim 50, wherein said at least onefunctional group is selected from hydroxyl groups.
 52. A cured coatingaccording to claim 1, wherein the components from which the compositionis formed comprise at least one material which has at least one reactivefunctional group which is blocked with a silyl group.
 53. A curedcoating according to claim 52, wherein the silyl blocking group has thefollowing structure (IX):

wherein each R¹, R² and R³, which may be identical or different, isselected from hydrogen, an alkyl group comprising from 1 to 18 carbonatoms, a phenyl group, and an allyl group.
 54. A cured coating accordingto claim 52, wherein the at least one reactive functional group isselected from a hydroxyl group, a carboxyl group, a carbamate group, andan amide group.
 55. A cured coating according to claim 52 comprising atleast one compound which can be reacted with the functional group toform the silyl group, wherein the at least one compound is selected fromhexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine,t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride,hexamethyl disilylazide, hexamethyl disiloxane, trimethylsilyl triflate,hexamethyldisilyl acetamide and mixtures of any of the foregoing.
 56. Acured coating according to claim 52, wherein the at least one materialcomprises at least one linkage selected from an ester linkage, anurethane linkage, a urea linkage, an amide linkage, a siloxane linkageand an ether linkage.
 57. A cured coating according to claim 52, whereinthe at least one material comprises a reaction product having thefollowing structure structure (X):


58. A cured coating according to claim 1, wherein the cured coating hasan initial scratch resistance value such that after scratch testinggreater than 50 percent of the initial 20° gloss is retained.
 59. Acured coating according to claim 1, wherein the cured coating has aretained scratch resistance value such that after scratch testinggreater than 30 percent of the initial 20° gloss is retained.
 60. Acured coating according to claim 59, wherein the cured coating has aretained scratch resistance value such that after scratch testinggreater than 40 percent of the initial 20° gloss is retained.
 61. Acured coating according to claim 1, wherein the cured coating has aconcentration of particles within a surface region thereof which isgreater than a concentration of particles within a bulk region thereof.62. A cured coating according to claim 1, wherein the coating isthermally cured.
 63. A cured coating according to claim 1, wherein thecoating is cured by exposure to ionizing radiation.
 64. A cured coatingaccording to claim 1, wherein the coating is cured by exposure toactinic radiation.
 65. A cured coating according to claim 1, wherein thecoating is cured by exposure to (1) ionizing radiation or actinicradiation and (2) thermal energy.